Comb-shaped structure polymer, preparation method and application
1. A comb-structured polymer having a repeating structural unit represented by the following formula I:
in the formula I, R1Is H or alkyl, preferably H or C1-16Alkyl of R3Is C3-16Alkyl of R4For diisocyanate removal of the chain segments of the two terminal-NCO groups, R5Is a segment of a polyester polyol or polyether polyol, R2Is composed ofWherein m is 0-50, n is 0-50, preferably m is 2-20, and n is 2-20; p is 0-50, q is 0-50, preferably p is 2-20, and q is 2-20;
in the formula I, x is a natural number with a value of 0-60, y is a natural number with a value of 0-10, z is a natural number with a value of 0-30, and x, y and z are not zero at the same time; preferably, x is a natural number with a value of 20-50, y is a natural number with a value of 2-5, and z is a natural number with a value of 5-20.
2. The comb-structured polymer according to claim 1, wherein the polymer is obtained by reacting a main chain polymer 1 and a side chain polymer 2; the main chain polymer 1 is obtained by polymerization reaction of an unsaturated carboxylic acid monomer A, an unsaturated monomer B containing hydroxyl and an unsaturated olefin monomer C; the side chain polymer 2 is obtained by the polymerization reaction of an isocyanate monomer D and a polyalcohol monomer E.
3. The comb-structured polymer according to claim 2, wherein the weight average molecular weight of the polymer 1 is 1000 to 12000g/mol, preferably 3000 to 10000 g/mol; the weight average molecular weight of the polymer 2 is 1000-10000 g/mol, preferably 4000-8000 g/mol.
4. The comb-structured polymer according to claim 2, wherein the unsaturated carboxylic acid monomer A is one or more of acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, and fumaric acid; the unsaturated monomer B containing hydroxyl has one or more structures shown in the structural expression formula II or III as follows:
in the formula, m is 0-50, n is 0-50, preferably m is 2-20, and n is 2-20; p is 0-50, q is 0-50, preferably p is 2-20, and q is 2-20; the unsaturated olefin monomer C is selected from C5-18Is preferably C5-C10More preferably one or more of pentene, hexene, decene, heptene, diisobutylene.
5. The comb-structured polymer according to claim 4, wherein the isocyanate monomer D is selected from one or more of aromatic diisocyanate or aliphatic diisocyanate, preferably hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate; the polyalcohol monomer E is selected from polyester polyol or polyether polyol, preferably polyester polyol or polyether polyol with the molecular weight of 200-1000, more preferably one or more of polyethylene glycol, polypropylene glycol and poly epsilon-caprolactone glycol.
6. The comb-structured polymer according to any one of claims 2 to 5, wherein the total amount of all the monomers A, B, C, D, E in the polymer is 100%, and the respective amounts of the monomers in the polymerization reaction are as follows:
5 to 20% by weight, preferably 10 to 20% by weight, of unsaturated carboxylic monomers A,
5 to 30 wt.%, preferably 10 to 25 wt.%,
unsaturated olefin monomers C5-15 wt.%, preferably 5-10 wt.%;
isocyanate monomers D10-30% by weight, preferably 15-25%;
10 to 40 wt%, preferably 20 to 35 wt% of polyol monomer E.
7. A preparation method of the comb-structure polymer according to any one of claims 1 to 6, characterized by comprising the following steps:
1) in the presence of an organic solvent and an initiator, carrying out free radical polymerization on an unsaturated carboxylic acid monomer A, a hydroxyl-containing unsaturated monomer B and an unsaturated olefin monomer C to generate a main chain polymer 1;
2) under the action of a catalyst 1, reacting an isocyanate monomer D and a polyalcohol monomer E to generate a side chain polymer 2;
3) and (3) reacting hydroxyl in the main chain polymer 1 with isocyanate groups in the side chain polymer 2 under the action of a catalyst 2 to generate the comb-structure polymer.
8. The method for preparing the comb-structured polymer according to claim 7, wherein the reaction temperature in the steps 1), 2) and 3) is selected from 60-150 ℃, preferably 70-120 ℃;
preferably, the initiator is an organic initiator, more preferably one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, dilauroyl peroxide, dibenzoyl peroxide, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, or di-tert-butyl peroxide;
preferably, the catalyst 1 and the catalyst 2 are independently selected from one or more of organic tin, organic zinc, organic titanium or organic bismuth, more preferably one or more of dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, dibutyltin diacetate, dibutyltin dioleate, zinc isooctanoate, zinc neodecanoate, tetrabutyl titanate, bismuth neodecanoate, bismuth isooctanoate, bismuth laurate and bismuth naphthenate;
preferably, the initiator is used in an amount of 0.5 to 10 wt%, preferably 3 to 8 wt%, based on the total mass of the monomer A, B, C in step 1);
preferably, the catalyst 1 is used in an amount of 1 to 10 wt%, preferably 2 to 6 wt%, of the total mass of the monomer D, E in step 2);
preferably, the catalyst 2 is used in an amount of 1 to 10 wt%, preferably 2 to 8 wt%, of the total mass of all the monomers A, B, C, D, E.
9. The preparation method of the comb-shaped structure polymer according to claim 7 or 8, characterized in that after the polymerization reaction is finished, the solvent is removed by distillation under reduced pressure, and the solid content of the polymer is adjusted to 30-60 wt%, preferably 40-50 wt%, and the pH is 7-11, preferably 7-9.
10. Use of the comb-structured polymer according to any one of claims 1 to 6 as a dispersant for aqueous coatings, inks, leather, textile dyes, colour pastes, ceramics or cosmetic preparations.
Background
In the fields of paint, printing ink, color paste and the like, the dispersion of pigment and filler is an important technical link, and the dispersing agent is an auxiliary agent for dispersing and stabilizing the pigment and filler, and the action mechanism of the dispersing agent is that the dispersing agent is adsorbed on the surface of the pigment and filler through an anchoring group, and particles are kept stable through electrostatic repulsion and/or steric hindrance, so that the pigment and filler particles are uniformly distributed in a system.
With increasingly stringent environmental requirements, there is an increasing demand for aqueous dispersant products. The traditional aqueous dispersant is mainly polycarboxylate homopolymer, and the dispersant has poor anchoring effect, is easily influenced by factors such as temperature, pH and the like, does not contain steric hindrance effect and has poor stability. Polycarboxylate copolymer dispersants, while having steric hindrance, generally have uncontrollable molecular weights and structures, resulting in poor anchoring. Therefore, the traditional aqueous dispersant has poor stability to the pigment and filler, and the phenomenon of coarse pigment and filler can occur, so that a formula system is unstable and the performance is poor.
The comb copolymer dispersant can enable the anchoring group and the solvation chain to exist simultaneously through the molecular design of the main chain and the side chain, thereby showing excellent dispersing and stabilizing effects, being controllable in molecular weight and structure and narrower in molecular weight distribution, and being capable of improving the dispersing efficiency and stability of the pigment and filler in a system.
Patent CN1308560A discloses polymeric dispersants prepared by reacting polyisocyanates with one or more poly (oxyalkylene carboxyl) chains, but the dispersants can only be used in solvent-borne systems. Patent CN105111813A discloses a method for preparing polyurethane modified acrylate polymer dispersant for paint, the prepared polyurethane modified acrylate effectively reduces the system viscosity, but the polymer structure of the dispersant does not contain water-based chain, and can only be used in solvent-based system.
Disclosure of Invention
The invention aims to solve the technical problem of how to prepare a comb-shaped polymer dispersant which is suitable for an oily system and a water-based system and has good dispersibility and slurry stability.
In order to solve the technical problems, the invention provides a comb-shaped structure polymer, a preparation method and application. The polymer takes a chain segment containing carboxylic acid groups and ether groups as a hydrophilic main chain, takes a reaction chain segment of isocyanate and polyalcohol as a hydrophobic side chain, has controllable molecular weight of a comb-shaped structure, can be simultaneously suitable for dispersing an oil system and a water system, has good slurry stability, and can improve the appearance, the resistance and other properties of a dispersion system product.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a comb-structured polymer having a repeating structural unit represented by the following formula I:
in the formula I, R1Is H or alkyl, preferably H or C1-16Alkyl of R3Is C3-16Alkyl of R4For diisocyanate removal of the chain segments of the two terminal-NCO groups, R5Is a segment of a polyester polyol or polyether polyol, R2Is composed ofWherein m is 0-50, n is 0-50, preferably m is 2-20, and n is 2-20; p is 0-50, q is 0-50, preferably p is 2-20, and q is 2-20; r2The symbol at the right end of the expression-indicates the key position;
in the formula I, x is a natural number with a value of 0-60, y is a natural number with a value of 0-10, z is a natural number with a value of 0-30, and x, y and z are not zero at the same time; preferably, x is a natural number with a value of 20-50, y is a natural number with a value of 2-5, and z is a natural number with a value of 5-20.
Further, the polymer is obtained by reacting a main chain polymer 1 and a side chain polymer 2; the main chain polymer 1 is obtained by polymerization reaction of an unsaturated carboxylic acid monomer A, an unsaturated monomer B containing hydroxyl and an unsaturated olefin monomer C; the side chain polymer 2 is obtained by the polymerization reaction of an isocyanate monomer D and a polyalcohol monomer E. Through the molecular structure design, the polymer 1 contains hydroxyl groups, the polymer 2 contains isocyanate groups, the final comb-shaped copolymer is prepared from the polymer 1 and the polymer 2 through the reaction of the hydroxyl groups and the isocyanate groups, the reaction yield is high, and the prepared comb-shaped polymer shows excellent dispersion efficiency and slurry stability.
Further, the weight average molecular weight of the polymer 1 is 1000-12000 g/mol, preferably 3000-10000 g/mol; the weight average molecular weight of the polymer 2 is 1000-10000 g/mol, preferably 4000-8000 g/mol.
Through the design of the molecular weight and the proportion of the two polymers, the special molecular structure of the two polymers has stronger adsorption force on pigment and filler particles, and bridging flocculation of a dispersing agent among the particles is avoided; and the solvent has regular solvation chain segments, so that the utilization rate of the solvation chain segments is greatly improved, and a formed dispersion system is more stable.
Further, the unsaturated carboxylic acid monomer A is one or more of acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, crotonic acid, mesaconic acid, citraconic acid or fumaric acid; the unsaturated monomer B containing hydroxyl has one or more structures shown in structural expressions of the following formula II or formula III, wherein the structure shown in the formula II represents allyl polyoxyethylene polyoxypropylene ether, and the structure shown in the formula III represents polyoxyethylene polyoxypropylene methacrylate.
In the formula, m is 0-50, n is 0-50, preferably m is 2-20, and n is 2-20; p is 0-50, q is 0-50, preferably p is 2-20, and q is 2-20; the unsaturated olefin monomer C is selected from C5-18Is preferably C5-C10More preferably one or more of pentene, hexene, decene, heptene, diisobutylene.
Further, the isocyanate monomer D is selected from aromatic diisocyanate or aliphatic diisocyanate, preferably one or more of hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate; the polyalcohol monomer E is selected from polyester polyol or polyether polyol, preferably polyester polyol or polyether polyol with the molecular weight of 200-1000, more preferably one or more of polyethylene glycol, polypropylene glycol and poly epsilon-caprolactone glycol.
Further, in the polymer, the amount of each monomer used in the polymerization reaction is, based on the total amount of all the monomers A, B, C, D, E taken as 100%:
5 to 20% by weight, preferably 10 to 20% by weight, of unsaturated carboxylic monomers A,
5 to 30 wt.%, preferably 10 to 25 wt.%,
unsaturated olefin monomers C5-15 wt.%, preferably 5-10 wt.%;
isocyanate monomers D10-30% by weight, preferably 15-25%;
10 to 40 wt%, preferably 20 to 35 wt% of polyol monomer E.
A method for preparing the comb-structured polymer, which comprises the following steps:
1) in the presence of an organic solvent and an initiator, carrying out free radical polymerization on an unsaturated carboxylic acid monomer A, a hydroxyl-containing unsaturated monomer B and an unsaturated olefin monomer C to generate a main chain polymer 1;
2) under the action of a catalyst 1, reacting an isocyanate monomer D and a polyalcohol monomer E to generate a side chain polymer 2;
3) and (3) reacting hydroxyl in the main chain polymer 1 with isocyanate groups in the side chain polymer 2 under the action of a catalyst 2 to generate the comb-structure polymer.
Further, in order to ensure high monomer conversion and to make the molecular weight of the polymer within the preferable range of the present invention, the reaction temperature in the steps 1), 2) and 3) is independently selected from 60 to 150 ℃, preferably 70 to 120 ℃;
specifically, in step 1), in some examples, the polymerization reaction is performed by adding raw materials in the following manner: adding an organic solvent into a reactor with a heating device, a heat transferring device and a stirrer, heating to a reaction temperature, and simultaneously dropwise adding a mixed solution of an initiator, a monomer A, a monomer B and a monomer C into the reactor for 2-6h, preferably 3-5 h; after the dropwise addition, the reaction is finished after the heat preservation for 1 h.
Specifically, in step 2), in some examples, the polymerization reaction is performed by adding raw materials in the following manner: the monomer D, the monomer E and the catalyst are added into a reactor with a heating device, a heat transfer device and a stirrer, and after the temperature is raised to the reaction temperature, the reaction is carried out for 2 to 8 hours, preferably 3 to 6 hours.
Specifically, in step 3), in some examples, the polymerization reaction is performed by adding raw materials in the following manner: adding the polymer 1, the polymer 2 and the catalyst into a reactor with a heating device, a heat transferring device and a stirrer, heating to the reaction temperature, reacting, and reaching the end point after reacting for 5-8 h.
Preferably, the initiator is an organic initiator, more preferably one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, dilauroyl peroxide, dibenzoyl peroxide, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, or di-tert-butyl peroxide;
preferably, the catalyst 1 and the catalyst 2 are independently selected from one or more of organic tin, organic zinc, organic titanium or organic bismuth, more preferably one or more of dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, dibutyltin diacetate, dibutyltin dioleate, zinc isooctanoate, zinc neodecanoate, tetrabutyl titanate, bismuth neodecanoate, bismuth isooctanoate, bismuth laurate and bismuth naphthenate;
preferably, the initiator is used in an amount of 0.5 to 10 wt%, preferably 3 to 8 wt%, based on the total mass of the monomer A, B, C in step 1);
preferably, the catalyst 1 is used in an amount of 1 to 10 wt%, preferably 2 to 6 wt%, of the total mass of the monomer D, E in step 2);
preferably, the catalyst 2 is used in an amount of 1 to 10 wt%, preferably 2 to 8 wt%, of the total mass of all the monomers A, B, C, D, E.
Preferably, the organic solvent is selected from ketone, ester or alcohol ether solvents, and may further preferably be one or more of acetone, butanone, ethyl acetate, butyl acetate, propylene glycol methyl ether, propylene glycol butyl ether and dipropylene glycol methyl ether; the adding amount of the organic solvent in the step 1) is 150 percent, preferably 150 percent, of the total mass of the monomer A, B, C; the addition amount of the organic solvent is controlled within the range, so that the low viscosity in the polymerization process can be ensured, and the improvement of the conversion rate of the monomer is facilitated.
Further, after the polymerization reaction is finished, the solvent is distilled off under reduced pressure, water is added to adjust the solid content of the polymer to 30-60 wt%, preferably 40-50 wt%, and alkali is added to adjust the pH to 7-11, preferably 7-9. The alkali is selected from alkali metal hydroxide or organic amine, and can be one or more of sodium hydroxide, potassium hydroxide, ammonia water, triethylamine, N-dimethylethanolamine, diethylethanolamine and 2-amino-2-methylpropanol.
Due to the design of special structure, molecular weight and proportion, the comb-shaped structure polymer dispersant disclosed by the invention can disperse organic and inorganic pigments and fillers, has high dispersion efficiency and excellent slurry stability, and can improve the appearance, the resistance and other properties of a system.
The invention further provides application of the comb-structure polymer. The polymers are suitable as dispersants for all the uses known from the prior art, for example, the polymers can be used for preparing coatings, inks, leather, textile dyes, colour pastes, ceramics, cosmetic preparations and, preferably, in each case in the presence of solid pigments and fillers.
The comb-shaped polymer is particularly suitable to be used as a wetting agent and a dispersing agent of various pigments and fillers, wherein the pigments and fillers comprise inorganic pigments and fillers and organic pigments and fillers, and the inorganic pigments and fillers comprise carbon black, graphite, titanium dioxide, calcium oxide, talcum powder, zinc oxide, barium sulfate, iron oxide, manganese phosphate, cobalt aluminate, antimony oxide, chromium oxide and the like; the organic pigment fillers include, for example, mono-, di-, tri-and higher azo pigments, oxazines, dioxazines, thiazine pigments, phthalocyanines, ultramarine and other metal complex pigments, indigo pigments, methine pigments, anthraquinones, pyranthrone dyes, acridines, quinacridones, perylenes and other polycyclic carbonyl pigments. When the comb-structure polymer is used as a dispersing agent, the addition amount of the comb-structure polymer is 1-15 wt%, preferably 1-10 wt% of the mass of the pigment and filler.
The invention adopts the five monomers with the specific structure and proportion for copolymerization and modification to prepare the comb-shaped polymer dispersant. The different kinds of monomers respectively bring inorganic pigment and filler anchoring groups (such as carboxylic acid groups and ether groups), water-soluble solvating chains (segments containing carboxyl groups and ether groups) and organic pigment and filler anchoring groups (such as amide, acrylate and unsaturated olefin groups) to the polymer. Under the synergistic action of the monomers, the polymer can disperse the inorganic pigment and filler through electrostatic repulsion and can disperse the organic pigment and filler, and the stability of the pigment and filler in a system is greatly improved under the action of a solvation chain. In addition, as the polymer is comb-shaped, and the main chain and the side chain of the polymer have specially designed structures and molecular weights, the polymer not only has stronger adsorption force on pigment and filler particles, but also avoids bridging flocculation of the dispersing agent among the particles; and the solvent has more regular solvent chain segments, so that the utilization rate of the solvent chain segments is greatly improved. Therefore, the polymer shows excellent dispersion efficiency of inorganic and organic pigments and fillers and slurry stability.
The beneficial effects of the invention are embodied in the following aspects:
1. the polymer dispersant comprises a hydrophilic main chain and a hydrophobic side chain, and contains a long ether anchoring group, so that the polymer dispersant has applicability to both oily and aqueous systems, and is good in dispersing effect and slurry stability.
2. The hydrophilic main chain and the hydrophobic side chain contain reactive groups, the main chain and the side chain polymer structure can be prepared respectively through free radical polymerization, and then the main chain and the side chain react to generate the comb-shaped structure polymer.
3. The polymer dispersant can realize molecular structure design by adjusting the molecular weight and the proportion of the main chain polymer 1 and the side chain polymer 2, has improved dispersant performance, and is favorable for maintaining the stability of a dispersion system.
4. The polymer dispersant can be used for dispersing organic and inorganic pigments and fillers, has good compatibility with systems such as water-based paint, printing ink and the like, improves the dispersion efficiency and stability, and can bring important properties such as excellent gloss, color spreading, water resistance and the like to the systems.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The main raw material sources in the examples are as follows:
allyl polyoxyethylene polyoxypropylene ether APEG-200: molecular weight 200, Haian petrochemical
Allyl polyoxyethylene polyoxypropylene ether APEG-300: molecular weight 300, Haian petrochemical
Polyoxyethylene polyoxypropylene methacrylate mPEG-130: molecular weight 130, carbohydrate science
Methacrylic acid polyoxyethylene polyoxypropylene ester mPEG-350: molecular weight 350, carbohydrate science
4, 4' -diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2, 4-toluene diisocyanate: from Wanhua chemistry
PEG 200: polyethylene glycol, molecular weight 200, Haian petrochemical
PEG 400: polyethylene glycol, molecular weight 400, Haian petrochemical
PEG 800: polyethylene glycol, molecular weight 800, Haian petrochemical
PEG 1000: polyethylene glycol, molecular weight 1000, Haian petrochemical
hk-1120: polyester polyol, molecular weight 1000, Huaqian
Acrylic acid, methacrylic acid, crotonic acid, maleic acid: from Wanhua chemistry
Heptene, hexene, decene, diisobutylene: from Xin run chemical
Defoaming agent: foamex 825 available from Digao
Polyacrylic acid resin: ARCHSO 8016 from Vanhua chemistry
Leveling agent: glide 450 available from Digao
Other common raw materials are commercially available materials unless otherwise specified.
Second, the embodiment of the invention and the comparative example adopt the main testing apparatus and method:
the polymer weight average molecular weight was determined by GPC (gel permeation chromatography) and was designated Optilab T-Rex/Viscostar-II/HELEOS-II.
1# and 2# reactors: all are fixed bed kettle type reactors with the volume of 1L.
[ example 1 ]
250g of acetone were added to the # 1 reactor and heated to 70 ℃. 75g of acrylic acid, 200100 g of APEG-30 g, 30g of heptene and 6.5g of azobisisoheptonitrile are mixed and dripped into a reactor and dripped for 5 hours. After the dropwise addition, the reaction was terminated by keeping the temperature for 1 hour to prepare a main chain polymer 1, the weight average molecular weight of which was 7896g/mol by GPC.
60g of 4, 4' -diphenylmethane diisocyanate, PEG 1000120 g and 5g of zinc isooctanoate are added into a 2# reactor, the temperature is raised to 70 ℃, and the reaction is carried out for 5 hours. After the reaction was complete, a side chain polymer 2 was obtained, which had a weight average molecular weight of 9865g/mol as determined by GPC.
Adding all the prepared main chain polymer 1 into a No. 2 reactor, adding 10g of zinc isooctanoate, heating to 90 ℃, reacting for 5h, finishing the reaction, removing the solvent by reduced pressure distillation, and adding water and a sodium hydroxide solution until the solid content of the reaction liquid is 45% and the pH value is 8. The weight-average molecular weight of the polymer in GPC was 27530g/mol, the polymer content was 99.2%, and the reaction yield was > 99%.
[ example 2 ]
260g of butanone was added to reactor # 1 and heated to 80 ℃. 60g of methacrylic acid, 80g of APEG-30080g, 35g of hexene and 10g of azobisisovaleronitrile are mixed and dripped into a reactor, and the mixture is dripped for 3 hours. After the dropwise addition, the reaction was terminated by keeping the temperature for 1 hour to prepare a main chain polymer 1, the weight average molecular weight of which was 4135g/mol by GPC.
Adding 90g of hexamethylene diisocyanate, PEG 40095 g and 6g of zinc neodecanoate into a No. 2 reactor, heating to 90 ℃, and reacting for 6 h. After the reaction was complete, a side chain polymer 2 was obtained, which had a weight average molecular weight of 5978g/mol, as determined by GPC.
Adding the main chain polymer 1 into a No. 2 reactor, adding 15g of zinc neodecanoate, heating to 100 ℃, reacting for 6h, finishing the reaction, removing the solvent by reduced pressure distillation, and adding water and a sodium hydroxide solution until the solid content of the reaction solution is 48% and the pH value is 7. The weight-average molecular weight of the polymer in GPC measurement is 16018g/mol, the polymer content is 99.4%, and the reaction yield is more than 99%.
[ example 3 ]
150g of butyl acetate are introduced into the reactor # 1 and heated to 100 ℃. 50g of butenoic acid, 13040g of mPEG, 20g of decene and 8g of dilauroyl peroxide are mixed and dropwise added into a reactor for 4 hours. After the dropwise addition, the reaction was terminated by keeping the temperature for 1 hour to prepare a main chain polymer 1, the weight average molecular weight of which was 2644g/mol by GPC.
60g of isophorone diisocyanate, PEG 80090 g and 5g of bismuth isooctanoate are added into a No. 2 reactor, the temperature is raised to 100 ℃, and the reaction is carried out for 4 hours. After the reaction was complete, a side chain polymer 2 was obtained which had a weight average molecular weight of 7631g/mol as determined by GPC.
Adding the main chain polymer 1 into a No. 2 reactor, adding 10g of bismuth isooctanoate, heating to 120 ℃, reacting for 7h, finishing the reaction, removing the solvent by reduced pressure distillation, and adding water and a sodium hydroxide solution until the solid content of the reaction solution is 50% and the pH value is 9. The weight-average molecular weight of the polymer is 17878g/mol, the polymer content is 99.3 percent and the reaction yield is more than 99 percent according to GPC measurement.
[ example 4 ]
260g of ethyl acetate were added to the # 1 reactor and heated to 120 ℃. 80g of maleic acid, mPEG-35090g, 20g of diisobutylene and 2g of dibenzoyl peroxide are mixed and dripped into a reactor and dripped for 5 hours. After the dropwise addition, the reaction was finished by keeping the temperature for 1 hour to prepare a main chain polymer 1, and the weight average molecular weight of the polymer 1 was 9738g/mol by GPC.
70g of 2, 4-toluene diisocyanate, PEG 200120 g and 10g of zinc isooctanoate are added into a 2# reactor, the temperature is raised to 120 ℃, and the reaction is carried out for 4 hours. After the end of the reaction, a side-chain polymer 2 was obtained, which had a weight-average molecular weight of 2831g/mol according to GPC measurement.
Adding the main chain polymer 1 into a No. 2 reactor, adding 20g of zinc isooctanoate, heating to 90 ℃, reacting for 8 hours, finishing the reaction, removing the solvent by reduced pressure distillation, and adding water and a sodium hydroxide solution until the solid content of the reaction solution is 47% and the pH value is 7. The weight-average molecular weight of the polymer in GPC measurement is 15379g/mol, the polymer content is 99.3%, and the reaction yield is more than 99%.
[ example 5 ]
250g of acetone were added to the # 1 reactor and heated to 70 ℃. 75g of acrylic acid, 200100 g of APEG-30 g, 30g of heptene and 6.5g of azobisisoheptonitrile are mixed and dripped into a reactor and dripped for 5 hours. After the dropwise addition, the reaction was terminated by keeping the temperature for 1 hour to prepare a main chain polymer 1, the weight average molecular weight of which was 7893g/mol by GPC.
70g of 4, 4' -diphenylmethane diisocyanate, hk-1120110 g and 6g of zinc neodecanoate are added into a 2# reactor, the temperature is raised to 80 ℃, and the reaction is carried out for 5 hours. After the reaction was complete, a side chain polymer 2 was obtained, which had a weight average molecular weight of 6646g/mol by GPC.
Then, the prepared main chain polymer 1 is completely added into a 2# reactor, 12g of zinc isooctanoate is added, the temperature is raised to 95 ℃, the reaction is finished after 5h, the solvent is removed by reduced pressure distillation, and water and sodium hydroxide solution are added to adjust the solid content of the reaction liquid to be 45 percent, and the pH value is 8. The weight-average molecular weight of the polymer was 14530g/mol, the polymer content was 99.2% and the reaction yield was > 99% by GPC.
Comparative example 1 (No monomer B)
250g of acetone were added to the # 1 reactor and heated to 70 ℃. 75g of acrylic acid, 30g of heptene and 6.5g of azobisisoheptonitrile are mixed and added into a reactor dropwise for 5 hours. After the dropwise addition, the reaction was terminated by keeping the temperature for 1 hour to prepare a polymer A having a weight average molecular weight of 3244g/mol by GPC.
60g of 4, 4' -diphenylmethane diisocyanate, PEG 1000120 g and 5g of zinc isooctanoate are added into a 2# reactor, the temperature is raised to 70 ℃, and the reaction is carried out for 5 hours. After the reaction was complete, polymer B was obtained which had a weight average molecular weight of 9861g/mol, determined by GPC.
Adding the polymer A into a No. 2 reactor, adding 10g of zinc isooctanoate, heating to 90 ℃, reacting for 5h, removing the solvent by reduced pressure distillation after the reaction is finished, adding water and a sodium hydroxide solution to adjust the solid content of the solution to be 45 percent and the pH value to be 8. GPC determined that the resulting polymer had a weight average molecular weight of 3248g/mol and 9869g/mol, indicating that the comb polymer contemplated by the present invention was not prepared.
Comparative example 2 (No monomer D)
250g of acetone were added to the # 1 reactor and heated to 70 ℃. 75g of acrylic acid, 200100 g of APEG-30 g, 30g of heptene and 6.5g of azobisisoheptonitrile are mixed and dripped into a reactor and dripped for 5 hours. After the dropwise addition, the reaction was terminated by keeping the temperature for 1 hour to prepare a polymer A having a weight average molecular weight of 7896g/mol as measured by GPC.
Adding PEG 1000120 g into a No. 1 reactor, adding 10g of zinc isooctanoate, heating to 90 ℃, reacting for 5h, removing the solvent by reduced pressure distillation after the reaction is finished, and adding water and sodium hydroxide solution to adjust the solid content to 45 percent and the pH value to 8. GPC determined that the resulting weight average molecular weight of the polymer was both 7892g/mol and 1000g/mol, indicating that no comb-structured polymer as contemplated by the present invention was produced.
Comparative example 3 (Polymer 1, Polymer 2 blend ratio out of range)
250g of acetone were added to the # 1 reactor and heated to 70 ℃. 120g of acrylic acid, 20095 g of APEG-heptylene, 30g of heptene and 8g of azobisisoheptonitrile are mixed and dripped into a reactor and dripped for 5 hours. After the dropwise addition, the temperature is kept for 1h to finish the reaction, so that a polymer A is prepared, and the weight average molecular weight of the polymer is 7541g/mol through GPC measurement.
60g of 4, 4' -diphenylmethane diisocyanate, PEG 1000120 g and 5g of zinc isooctanoate are added into a 2# reactor, the temperature is raised to 70 ℃, and the reaction is carried out for 5 hours. After the reaction was complete, a polymer B was obtained, which had a weight average molecular weight of 9867g/mol, as determined by GPC.
Adding the polymer A into a No. 2 reactor, adding 10g of zinc isooctanoate, heating to 90 ℃, reacting for 5h, removing the solvent by reduced pressure distillation after the reaction is finished, and adding water and sodium hydroxide solution to adjust the solid content to be 45% and the pH value to be 8. The weight-average molecular weight of the obtained polymer was 17173g/mol, the polymer content was 99.1% and the reaction yield was > 99% by GPC.
Comparative example 4 (Polymer 1, Polymer 2 blend ratio out of range)
250g of acetone were added to the # 1 reactor and heated to 70 ℃. 75g of acrylic acid, 75g of APEG-200125 g of heptene, 15g of heptylene and 6.5g of azobisisoheptonitrile were mixed and added dropwise into a reactor for 5 hours. After the completion of the dropwise addition, the reaction was terminated by keeping the temperature for 1 hour to prepare a main chain polymer 1 having a weight average molecular weight of 10257g/mol as measured by GPC.
60g of 4, 4' -diphenylmethane diisocyanate, PEG 1000120 g and 5g of zinc isooctanoate are added into a 2# reactor, the temperature is raised to 70 ℃, and the reaction is carried out for 5 hours. After the reaction was complete, a side chain polymer 2 was obtained, which had a weight average molecular weight of 9867g/mol as determined by GPC.
Adding all the prepared main chain polymer 1 into a No. 2 reactor, adding 10g of zinc isooctanoate, heating to 90 ℃, reacting for 5h, finishing the reaction, removing the solvent by reduced pressure distillation, and adding water and a sodium hydroxide solution until the solid content of the reaction liquid is 45% and the pH value is 8. The weight-average molecular weight of the polymer is 20130g/mol, the polymer content is 99.2 percent and the reaction yield is more than 99 percent according to GPC test.
Comparative example 5 (Polymer 1, Polymer 2 molecular weight out of range)
250g of acetone were added to the # 1 reactor and heated to 70 ℃. 75g of acrylic acid, 200100 g of APEG-200100 g, 30g of heptene and 1g of azodiisoheptonitrile are added into the reactor dropwise for 5 hours. After the dropwise addition, the reaction was terminated by keeping the temperature for 1 hour to prepare a polymer A having a weight average molecular weight of 18532g/mol according to GPC measurement.
60g of 4, 4' -diphenylmethane diisocyanate, PEG 1000120 g and 5g of zinc isooctanoate are added into a 2# reactor, the temperature is raised to 70 ℃, and the reaction is carried out for 5 hours. After the reaction was complete, a polymer B was obtained, which had a weight average molecular weight of 9861g/mol, as determined by GPC.
Adding the polymer A into a No. 2 reactor, adding 10g of zinc isooctanoate, heating to 90 ℃, reacting for 5h, removing the solvent by reduced pressure distillation after the reaction is finished, and adding water and sodium hydroxide solution to adjust the solid content to be 45% and the pH value to be 8. The weight-average molecular weight of the obtained polymer was 37835g/mol, the polymer content was 99.2% and the reaction yield was > 99% by GPC.
Application testing
In order to test the dispersing performance of the polymer obtained in each example and comparative example of the present invention as a dispersant, the application performance of the polymer in an inorganic pigment and an organic pigment is respectively tested.
(1) Performance test of inorganic pigment and filler
First, resin-free inorganic pigment concentrates were prepared according to the formulations of table 1. The millbase is dispersed in a shaker for 1 hour with the aid of zirconium beads. The millbase is then filtered and stored at room temperature overnight.
TABLE 1 preparation of inorganic pigment concentrates
Name of material
Mass/g
Dispersing agent
0.82
Water (W)
16.5
Titanium white powder
32.5
Defoaming agent
0.18
Zirconium bead
100
Total of
150
Paint A was then formulated according to the formulation in Table 2, starting from the inorganic pigment concentrate prepared as described above, and the components of paint A were mixed in a high shear mixer at 2000rpm/23 ℃ for 5 minutes.
TABLE 2 preparation formulation for paint A
Name of material
Mass/g
Inorganic pigment concentrates
21.0
Heavy calcium carbonate
15.4
Talcum powder
4.0
Polyacrylic acid resin
34.3
Defoaming agent
0.4
Propylene glycol
1.0
Dipropylene glycol methyl ether
1.0
Leveling agent
1.5
Water (W)
1.4
Total of
80.0
The inorganic pigment concentrates prepared in table 1 were subjected to a viscosity test and a storage stability test; the paints prepared in table 2 were tested for hiding, see table 3:
the rheological behaviour of the pigment concentrate is measured using a Brookfield viscometer apparatus at a speed of 20rpm, with lower viscosity indicating higher dispersing properties of the dispersant;
the storage stability of the pigment concentrates is tested by delamination during storage, the longer the storage time the better the stability of the dispersant.
The prepared paint A was applied to a black and white cardboard with a film thickness of 250 μm, and the hiding of the paint was determined according to ISO 6504-1, the higher the hiding contrast ratio indicating the better the dispersing properties of the dispersant.
TABLE 3 test results for inorganic pigment concentrates and paint A
The inorganic pigment concentrate prepared without the addition of the polymeric dispersant and paint A were also used as blank controls, the pigment concentrate viscosity test data was 12362cp, the storage stability test result was < 1d, and the paint hiding contrast ratio was 81.1%. As can be seen from the test results in table 3, the comb-structured polymer prepared according to the invention has a lower viscosity, a better storage stability and a higher hiding contrast ratio than the products in the comparative examples.
(2) Organic pigment and filler performance test
First, resin-free organic pigment concentrates were prepared according to the formulations in table 4. The millbase is dispersed in a shaker for 1 hour with the aid of zirconium beads. The millbase is then filtered and stored at room temperature overnight.
TABLE 4 preparation of organic pigment concentrates
Name of material
Mass/g
Dispersing agent
2.5
Water (W)
22.2
Phthalocyanine blue
25
Defoaming agent
0.2
Zirconium bead
100
Total of
150
Paint B was then formulated according to the formulation in Table 5, starting from the organic pigment concentrate prepared as described above, and the components of paint B after mixing were mixed in a high shear mixer at 2000rpm/23 ℃ for 5 minutes.
TABLE 5 preparation formulation for paint B
The organic pigment concentrates prepared in table 4 were subjected to a viscosity test and a storage stability test; paint B prepared in table 5 was tested for hiding, see table 6:
the rheological behaviour of the pigment concentrate is measured using a Brookfield viscometer apparatus at a speed of 20rpm, with lower viscosity indicating higher dispersing properties of the dispersant;
the storage stability of the pigment concentrates is tested by delamination during storage, the longer the storage time the better the stability of the dispersant.
The paint B was tested for color development according to GB/T5211.19-1988 using the finger research method, with a smaller color difference indicating better color development of the dispersant.
TABLE 6 test results for organic pigment concentrates and paint B
Examples
Viscosity/cp
Storage stability/d
Color difference/. DELTA.E
No dispersant
14325
<1
9.5
Example 1
252
5
1.14
Example 2
356
6
1.35
Example 3
187
6
0.92
Example 4
240
6
1.15
Example 5
201
6
1.03
Comparative example 1
8422
2
6.14
Comparative example 2
8329
1
5.77
Comparative example 3
2687
2
4.34
Comparative example 4
1011
2
3.59
Comparative example 5
5543
2
4.78
The organic pigment concentrate prepared without the addition of the polymeric dispersant and paint B were also used as blank controls, with the pigment concentrate viscosity test data being 14325cp, the storage stability test result being < 1d, and the paint color difference being 9.5. As can be seen from the test results in table 6, the comb-structured polymer prepared according to the present invention has lower viscosity, more excellent storage stability and better color development compared to the product in each comparative example.
From the above, although some test results inevitably have errors within a certain range, the following conclusions can be clearly drawn: the comb-shaped polymer provided by the invention has the advantages that due to the special design of the structure, no matter inorganic pigments and fillers or organic pigments and fillers are dispersed, the dispersing performance, the suspension stability and the color development of the colored paint are all obvious advantages.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
