1. A wash resistant polyurethane foam characterized by: the composition is prepared from the following components in parts by weight: 50-80 parts of isocyanate, 60-90 parts of polyether polyol, 2-4 parts of foaming auxiliary agent, 3-5 parts of water, 15-20 parts of sulfhydryl modified soybean oil polyol, 10-20 parts of alkenyl-containing silane and 2-4 parts of photoinitiator.

2. A wash resistant polyurethane foam as claimed in claim 1 wherein: the composition is prepared from the following components in parts by weight: 60-70 parts of isocyanate, 70-80 parts of polyether polyol, 2-2.5 parts of foaming auxiliary agent, 3.5-4.5 parts of water, 17-19 parts of sulfhydryl modified soybean oil polyol, 14-16 parts of alkenyl-containing silane and 2.5-3.5 parts of photoinitiator.

3. The wash-resistant polyurethane foam material as claimed in claim 1, wherein the preparation method of the thiol-modified soybean oil polyol comprises the following steps:

s1, uniformly mixing 15-18 parts by weight of mercaptoethanol, 0.2-0.3 part by weight of 2-hydroxy-2-methyl-phenyl-acetone and 11-14 parts by weight of acetone to obtain a mixed solution;

s2, adding 4-6 parts by weight of soybean oil into the mixed solution to obtain a reaction solution;

and S3, placing the reaction solution under ultraviolet irradiation for reaction for 4-6h, and extracting, washing and drying the reaction product to obtain the sulfhydryl modified soybean oil polyol.

4. A wash resistant polyurethane foam as claimed in claim 1 wherein: the alkenyl-containing silane is one of dimethyl divinyl silane or tetramethyl divinyl disiloxane.

5. A wash resistant polyurethane foam as claimed in claim 1 wherein: the photoinitiator is a polysiloxane photoinitiator.

6. The wash-resistant polyurethane foam material as claimed in claim 5, wherein said polysiloxane photoinitiator is prepared by a process comprising the steps of:

uniformly mixing 18-22 parts by weight of 1-hydroxycyclohexyl benzophenone, 13-17 parts by weight of triethylamine and 300 parts by weight of dichloromethane 220-one to obtain a solution A;

maintaining the solution A at 0-5 ℃, adding 8-12 parts by weight of acryloyl chloride into the solution A, and reacting at room temperature for 22-28h to obtain a solution B;

filtering, washing, distilling and purifying the solution B to obtain a solid product;

and dissolving 8-12 parts by weight of solid product and 4-6 parts by weight of amino silicone oil in ethyl acetate, reacting for 3-6h, and purifying the reaction product to obtain the polysiloxane photoinitiator.

7. A wash resistant polyurethane foam as claimed in claim 1 wherein: the foaming auxiliary agent comprises an amine catalyst, stannous octoate, a foam stabilizer and a cell opening agent.

8. A process for preparing a wash resistant polyurethane foam material as set forth in claim 1, including the steps of:

according to the proportion, uniformly mixing the mercapto-modified soybean oil polyol, alkenyl-containing silane and a photoinitiator, and reacting for 3-5h under the irradiation of ultraviolet light to obtain the silicone-containing soybean oil polyol;

uniformly mixing polyether polyol, a foaming auxiliary agent, water and the silane-containing soybean oil polyol to obtain a mixture;

and mixing isocyanate with the mixture, stirring for 13-17s at 4000-6000 r/min, carrying out foaming reaction at 70-90 ℃ for 1-1.4h, and cooling to room temperature to obtain the cleaning-resistant polyurethane foam material.

Background

The polyurethane foam material is a high molecular polymer prepared by taking isocyanate and polyether as main raw materials and adopting a specific foaming process under the action of various auxiliary agents such as a foaming agent, a catalyst, a flame retardant and the like. The polyurethane foam material comprises a polyurethane soft foam body and a polyurethane hard foam body, and the polyurethane soft foam body has excellent rebound resilience and can be used for manufacturing household articles such as sofa cushions, mattresses and the like.

In a related art, patent publication No. CN106800635A discloses a medium density polyurethane soft foam formula, which is based on 100 parts of polypropylene glycol, and comprises the following components in parts by weight: toluene diisocyanate: 50-60 parts; amine catalyst: 0.1 to 0.5 portion; stannous octoate: 0.1 to 0.2 portion; surfactant (b): 1-1.5 parts; water: 4 parts. The medium-density polyurethane soft foam has better softness, flexibility and elasticity, and can be used for manufacturing household articles such as sofa cushions and the like.

In view of the above-mentioned related arts, the inventors consider that the medium-density flexible polyurethane foam material needs to be kneaded in a cleaning solution during a cleaning process, and the medium-density flexible polyurethane foam material is easily damaged.

Disclosure of Invention

In order to solve the problem that the polyurethane foam material is easy to damage in the cleaning process, the application provides a cleaning-resistant polyurethane foam material and a preparation method thereof.

In a first aspect, the application provides a cleaning-resistant polyurethane foam material, which adopts the following technical scheme:

a washing-resistant polyurethane foam material is prepared from the following components in parts by weight: 50-80 parts of isocyanate, 60-90 parts of polyether polyol, 2-4 parts of foaming auxiliary agent, 3-5 parts of water, 15-20 parts of sulfhydryl modified soybean oil polyol, 10-20 parts of alkenyl-containing silane and 2-4 parts of photoinitiator.

By adopting the technical scheme, the sulfydryl modified soybean oil polyol is hydroxylated soybean oil containing sulfydryl groups, and under the irradiation of ultraviolet light, the photoinitiator can initiate carbon-carbon double bonds and the sulfydryl groups to generate sulfydryl-alkene light click reaction, so that the silane groups are linked to the sulfydryl modified soybean oil; the sulfydryl modified soybean oil and isocyanate are subjected to foaming reaction to obtain a polyurethane foam material containing silane groups, and the silane groups can reduce the surface energy of the polyurethane foam material, improve the hydrophobicity of the polyurethane foam material and contribute to reducing the damage of water to the polyurethane foam material in the cleaning process;

in addition, as the mercapto-modified soybean oil polyol contains chain-end primary hydroxyl, the primary hydroxyl has high activity and high reaction rate with isocyanic acid radical, more crosslinking structures can be generated, the tensile strength of the generated polyurethane foam material is improved, the polyurethane foam material has higher toughness, and the damage of the polyurethane foam due to kneading can be reduced;

therefore, the present application can improve the problem that the polyurethane foam is easily damaged during the cleaning process.

Preferably, the washing-resistant polyurethane foam material is prepared from the following components in parts by weight: 60-70 parts of isocyanate, 70-80 parts of polyether polyol, 2-2.5 parts of foaming auxiliary agent, 3.5-4.5 parts of water, 17-19 parts of sulfhydryl modified soybean oil polyol, 14-16 parts of alkenyl-containing silane and 2.5-3.5 parts of photoinitiator.

By adopting the technical scheme, the hydrophobic property and the water resistance of the polyurethane foam material are further improved under the above proportion, and the damage of the polyurethane foam material in the cleaning process is reduced.

Preferably, the preparation method of the sulfhydryl modified soybean oil polyol comprises the following steps:

s1, uniformly mixing 15-18 parts by weight of mercaptoethanol, 0.2-0.3 part by weight of 2-hydroxy-2-methyl-phenyl-acetone and 11-14 parts by weight of acetone to obtain a mixed solution;

s2, adding 4-6 parts by weight of soybean oil into the mixed solution to obtain a reaction solution;

and S3, placing the reaction solution under ultraviolet irradiation for reaction for 4-6h, and extracting, washing and drying the reaction product to obtain the sulfhydryl modified soybean oil polyol.

By adopting the technical scheme, under the irradiation of ultraviolet light, 2-hydroxy-2-methyl-phenyl-acetone can initiate sulfydryl-alkene light click reaction, which is beneficial to improving the conversion rate of carbon-carbon double bonds of soybean oil and is convenient for obtaining purer soybean oil polyol.

Preferably, the alkenyl-containing silane is one of dimethyldivinylsilane or tetramethyldivinyldisiloxane.

By adopting the technical scheme, the molecular chain of the alkenyl-containing silane contains two carbon-carbon double bonds, and the two carbon-carbon double bonds can react with the mercapto group, so that more crosslinking structures can be generated, and the tensile strength and the toughness of the polyurethane foam material are improved.

Preferably, the photoinitiator is a polysiloxane photoinitiator.

By adopting the technical scheme, the polysiloxane photoinitiator is obtained by introducing a common micromolecular photoinitiator into polysiloxane, and the polysiloxane photoinitiator can not only initiate the reaction between sulfydryl and carbon-carbon double bonds, but also improve the compatibility among raw materials, further reduce the surface energy of the prepared polyurethane foam material and contribute to improving the water resistance and the hydrophobicity of the polyurethane foam material.

Preferably, the preparation method of the polysiloxane photoinitiator comprises the following steps:

uniformly mixing 18-22 parts by weight of 1-hydroxycyclohexyl benzophenone, 13-17 parts by weight of triethylamine and 300 parts by weight of dichloromethane 220-one to obtain a solution A;

maintaining the solution A at 0-5 ℃, adding 8-12 parts by weight of acryloyl chloride into the solution A, and reacting at room temperature for 22-28h to obtain a solution B;

filtering, washing, distilling and purifying the solution B to obtain a solid product;

and dissolving 8-12 parts by weight of solid product and 4-6 parts by weight of amino silicone oil in ethyl acetate, reacting for 3-6h, and purifying the reaction product to obtain the polysiloxane photoinitiator.

By adopting the technical scheme, the preparation method has mild conditions, and both the intermediate product and the final product are purified in the preparation process, thereby being beneficial to improving the purity of the polysiloxane photoinitiator and reducing the adverse effects of the solvent and the by-products.

Preferably, the foaming aid comprises an amine catalyst, stannous octoate, a foam stabilizer and a cell opening agent.

By adopting the technical scheme, the amine catalyst and stannous octoate are beneficial to catalyzing isocyanate to carry out foaming reaction; the foam stabilizer can reduce the surface tension of the polyurethane raw material mixture and is beneficial to opening and bursting holes at the later foaming stage; the cell opening agent can promote cell breakage and contribute to the improvement of the elasticity of the polyurethane foam.

In a second aspect, the application provides a preparation method of a cleaning-resistant polyurethane foam material, which adopts the following technical scheme:

a preparation method of a cleaning-resistant polyurethane foam material comprises the following steps:

according to the proportion, uniformly mixing the mercapto-modified soybean oil polyol, alkenyl-containing silane and a photoinitiator, and reacting for 3-5h under the irradiation of ultraviolet light to obtain the silicone-containing soybean oil polyol;

uniformly mixing polyether polyol, a foaming auxiliary agent, water and the silane-containing soybean oil polyol to obtain a mixture; and mixing isocyanate with the mixture, stirring for 13-17s at 4000-6000 r/min, carrying out foaming reaction at 70-90 ℃ for 1-1.4h, and cooling to room temperature to obtain the cleaning-resistant polyurethane foam material.

By adopting the technical scheme, the sulfydryl modified soybean oil polyol, the alkenyl-containing silane and the photoinitiator are reacted, so that the generation of the soybean oil polyol containing the silane is facilitated, and the influence of the alkenyl-containing silane on the foaming reaction is reduced; the isocyanate is mixed with the mixture and then stirred vigorously, which helps to mix the isocyanate and the mixture uniformly in a short time and helps to prepare a wash-resistant polyurethane foam material with uniform texture.

In summary, the present application has the following beneficial effects:

1. due to the adoption of the sulfhydryl modified soybean oil polyalcohol, the alkenyl-containing silane and the photoinitiator, the hydrophobicity, the water resistance and the toughness of the polyurethane foam material can be improved, and the problem that the polyurethane foam material is easy to damage in the cleaning process is solved;

2. dimethyl divinyl silane or tetramethyl divinyl disiloxane is preferably adopted in the application, and because the dimethyl divinyl silane and the tetramethyl divinyl disiloxane both contain two carbon-carbon double bonds, the crosslinking density and the tensile strength of the polyurethane foam material are improved;

3. according to the method, the soybean oil polyol containing the silane group is prepared firstly, so that the influence of the silane containing the alkene on the foaming reaction is reduced, the isocyanate and the mixture are uniformly mixed in a short time, and the clean-resistant polyurethane foam material with uniform texture is prepared.

Detailed Description

The present application will be described in further detail with reference to examples.

The starting materials used in the examples of the present application are all commercially available. Wherein mercaptoethanol is obtained from LA-W21 of Shandong Liang New Material science and technology Limited, 2-hydroxy-2-methyl-phenyl-acetone is obtained from 1173 of Shanghai Aladdin reagent, acetone is obtained from Toguan Fengsheng science and technology Limited, soybean oil is refined soybean oil obtained from Guangzhou Wanniilai chemical industry Limited, 1-hydroxycyclohexyl phenyl ketone is obtained from Hubei Jianchu biological medicine Limited, triethylamine is obtained from Nanjing Runsheng petrochemical industry Limited, dichloromethane is obtained from Shandong Yiwei chemical industry technology Limited, acryloyl chloride and amino silicone oil are obtained from Jiangsu Runfeng synthesis technology Limited, and isocyanate is W8019 type dimethyl methane diisocyanate obtained from Wanhua chemical group Limited; the polyether polyol is EP-330N available from Shandong Lanxingdong chemical company, the amine catalyst is A33 available from national pharmaceutical group chemical reagent Co., Ltd, the stannous octoate is industrial grade stannous octoate available from Jinhui Chuan chemical company, Jinan, China, the foam stabilizer is B8002 available from Yingchuang Texaco investment Co., Ltd, the cell opener is Y-1900 available from Korean SKC Co., Ltd, the dimethyldivinylsilane is available from Suzhou Siloso new material Co., Ltd, the tetramethyldivinyldisiloxane is industrial grade tetramethyldivinyldisiloxane available from Shandong national chemical industry Co., Ltd, and the vinyltrimethoxysilane is available from Shanghai Aladdin reagent Co., Ltd.

Preparation of thiol-modified Soybean oil polyol

Preparation examples 1 to 3

As shown in Table I, the preparation examples 1 to 3 are different in the ratio of the raw materials.

The following will describe in detail the production example 1 as an example.

The sulfhydryl modified soybean oil polyalcohol is prepared by the following steps:

s1, adding mercaptoethanol, 2-hydroxy-2-methyl-phenyl-acetone and acetone into a transparent reactor according to the proportion, and stirring for 3min at 150r/min to obtain a mixed solution;

s2, dripping soybean oil into the transparent reactor at a speed of 2 drops/second at 150r/min, and obtaining reaction liquid after finishing dripping soybean oil;

s3, placing the transparent reactor under the irradiation of an ultraviolet lamp in a darkroom environment at 25 ℃, reacting for 5 hours, adding the reaction product and 30L of ethyl acetate into a mixer, stirring uniformly, adding 30L of saturated sodium chloride solution into the mixer for extraction, taking out an extracted upper organic phase, centrifuging for 15min at 8000r/min, washing the centrifuged liquid with n-hexane, and drying the washed liquid at 50 ℃ to obtain the sulfhydryl modified soybean oil polyol.

Wherein the power of the ultraviolet lamp is 30kw/h, and the wavelength of the ultraviolet light emitted by the ultraviolet lamp is 284-365 nm.

Watch 1

Preparation of polysiloxane photoinitiator

Preparation examples 4 to 6

As shown in Table II, the differences between the preparation examples 4 to 6 are in the ratios of the raw materials.

The following will describe preparation example 4 in detail.

The polysiloxane photoinitiator was prepared as follows:

adding 1-hydroxycyclohexyl benzophenone, triethylamine and dichloromethane into a reactor according to the proportion, uniformly stirring, and dissolving the 1-hydroxycyclohexyl benzophenone and the triethylamine into the dichloromethane to obtain a solution A;

controlling the temperature of the solution A in the reactor within the range of 0-5 ℃, then dropwise adding acryloyl chloride into the solution A at the speed of 2 drops/second, and after dropwise adding, controlling the temperature in the reactor at 25 ℃ for reacting for 24 hours to obtain a solution B;

filtering the solution B, washing the filtered filtrate for 3 times by using 1mol/L sodium chloride solution, 1mol/L hydrochloric acid solution and deionized water respectively, distilling the washed solution under vacuum to remove the solvent in the solution, and recrystallizing and purifying the distilled solid by using ethanol to obtain a solid product;

adding 10kg of solid product and 100L of ethyl acetate into a mixer, controlling the temperature in the mixer to be 30 ℃ when the solid product is dissolved in the ethyl acetate, adding 5kg of amino silicone oil into the mixer for reaction for 4 hours, and purifying the obtained reaction product by a gel column to obtain the polysiloxane photoinitiator.

Wherein the developing agent used for purifying by the gel column is a mixed solution of ethyl acetate and n-hexane in a volume ratio of 2: 1.

Watch two

Examples

Examples 1 to 5

As shown in Table three, examples 1-5 differ in the ratio of the raw materials.

The following will explain in detail by taking example 1 as an example.

A wash-resistant polyurethane foam is prepared by the following steps:

adding the sulfhydryl modified soybean oil polyalcohol, the alkenyl-containing silane and the photoinitiator into a transparent reactor according to the proportion, and uniformly stirring at 150 r/min; then, under the condition of a darkroom, the transparent reactor is placed under an ultraviolet lamp, and reacts for 4 hours under the irradiation of ultraviolet light emitted by the ultraviolet lamp to obtain the silicone-containing soybean oil polyol; wherein the power of the ultraviolet lamp is 30kw/h, and the wavelength of the ultraviolet light emitted by the ultraviolet lamp is 284-365 nm;

then adding polyether polyol, a foaming auxiliary agent, water and the silane-containing soybean oil polyol into a polytetrafluoroethylene container, and stirring for 5min at 3000r/min to obtain a mixture;

and adding isocyanate into the mixture, stirring for 15s at 5000r/min, pouring into a polytetrafluoroethylene mold, then placing the mold into an oven, keeping the temperature in the oven at 80 ℃, carrying out foaming reaction for 1.2h, and cooling the reaction product to room temperature to obtain the cleaning-resistant polyurethane foam material.

Watch III

Examples 6 to 10

As shown in Table four, examples 6 to 10 are different from example 5 in the point that the raw materials used are different.

Watch four

Example 11

This example differs from example 5 in that the photoinitiator prepared in preparation 4 is replaced by the same amount of 2-hydroxy-2-methyl-phenyl-acetone.

Example 12

This example differs from example 5 in that dimethyldivinylsilane is replaced by the same amount of vinyltrimethoxysilane.

Comparative example

Comparative example 1

An ethanol-soybean oil-based polyol polyurethane foam is prepared according to the following steps: according to the weight parts, 10 parts of ethanol-soybean oil-based polyol (E-PUF), 90 parts of petroleum-based polyether polyol, 90 parts of isocyanate, 1 part of water, 2.5 parts of silicone oil, 1 part of amine catalyst and 0.3 part of organic tin catalyst are taken in sequence; pouring ethanol-soybean oil-based polyol, petroleum-based polyether polyol, water, silicone oil, amine catalyst and organic tin catalyst into a clean storage dish, adjusting the temperature to 25 ℃, stirring and mixing the materials for 30s at the rotating speed of 800 plus one year/min by using a stirrer, adjusting the temperature of isocyanate to 25 ℃, preserving the heat for 10-20min, pouring the two parts of materials into a temperature-controlled stirrer, setting the temperature of the temperature-controlled stirrer to 25 ℃, 2000r/min, stirring and reacting for 8-10s, injecting the uniformly mixed materials into a preheated mold at 25 ℃, preserving the heat, standing and molding, and demolding to obtain the ethanol-soybean oil-based polyol polyurethane foam.

Comparative examples 2 to 3

As shown in Table five, comparative examples 2 to 3 are different in the compounding ratio of the raw materials from example 1.

Watch five

Comparative example 4

This example differs from example 5 in that it does not contain the mercapto-modified soybean oil polyol.

Comparative example 5

This example differs from example 5 in that no alkenyl-containing silane is included.

Comparative example 6

This example differs from example 5 in that no photoinitiator is present.

Performance test

The following property tests were performed on the foam samples provided in examples 1 to 12 and comparative examples 1 to 6.

Measuring the static contact angle of the foam sample by adopting an OCA40 type optical contact angle measuring instrument to represent the hydrophobicity of the foam sample; wherein, the probe liquid is ultrapure water, and three parallel tests are carried out at 25 ℃ and an average value is taken.

A5967X type double-column type experiment system is adopted to test the mechanical property of the foam sample. Before testing, the foam sample is cut into dumbbell-shaped sheets with the width of 2mm and the length of 10mm, the tensile rate is set to be 10mm/min at the relative humidity of 65-85% and the temperature of 25 ℃, and the tensile strength of the foam sample is tested.

The foam samples were tested for ball rebound according to ASTM D3574 test method for Soft cellular Material Flat bonded and molded urethane foams. The foam sample is made into a sample with the size of 100mm multiplied by 50mm, a steel ball with the diameter of 16mm is freely dropped on the surface of the sample from the distance of 460mm through a PMLQ-500 type sponge ball dropping rebound tester, the maximum rebound height is recorded, the ratio of the rebound height of the steel ball to the initial height is the percent of the rebound of the steel ball, and the larger the percent of the rebound of the steel ball is, the better the rebound performance of the foam sample is.

The test results are shown in table six.

Watch six

Combining examples 1-5 and comparative example 1 and combining table six, it can be seen that the foam samples of examples 1-5 all had larger static contact angles and greater than 90 ° compared to the foam sample of comparative example 1, which demonstrates that the foam samples of examples 1-5 are more hydrophobic, helping to reduce water damage to the foam samples; furthermore, the foam samples of examples 1-5 had greater tensile strength and percent rebound, which indicates that the foam samples of examples 1-5 had better toughness and resiliency.

As can be seen by combining examples 5-7 with Table VI, the foam samples of examples 6-7 exhibited less change in static contact angle, tensile strength and percent rebound as compared to the foam sample of example five, indicating that the thiol-modified soybean oil polyols prepared under the conditions of preparation examples 1-3 all contributed to the preparation of clean-resistant polyurethane foams with improved hydrophobicity, toughness and resiliency.

Combining examples 5, 8 and 12 with Table six, it can be seen that the foam samples of example 8 did not change much in static contact angle, tensile strength and percent rebound compared to the foam samples of example five, and the foam samples of example 12 did not change much in static contact angle, tensile strength and percent rebound, but the foam samples of example 12 did not change much in static contact angle, tensile strength and percent rebound compared to comparative example 1, indicating that dimethyldivinylsilane, tetramethyldivinyldisiloxane and vinyltrimethoxysilane all contribute to the improvement in hydrophobicity and toughness of the foam samples and that dimethyldivinylsilane and tetramethyldivinyldisiloxane work better.

Combining examples 5, 9-11, and comparative example 1 with Table six, it can be seen that the foam samples of examples 5, 9-11 all had larger static contact angles, tensile strengths, and percent rebound than the foam sample of comparative example 1, indicating that both the polysiloxane photoinitiator and 2-hydroxy-2-methyl-phenyl-acetone contribute to the preparation of clean-up resistant polyurethane foams with better hydrophobicity, toughness, and elasticity.

The foam samples of examples 9-10 did not change much in static contact angle, tensile strength and percent rebound compared to the foam sample of example five, the foam sample of example 11 did not change much in tensile strength and percent rebound, but the foam sample of example 11 did not change much in static contact angle, indicating that the polysiloxane photoinitiator helps to further increase the hydrophobicity of the polyurethane foam compared to 2-hydroxy-2-methyl-phenyl-acetone.

Combining examples 1-5 and comparative examples 2-3 with Table six, it can be seen that the foam samples of comparative examples 2-3 have lower static contact angles, tensile strengths and percent rebound than the foam sample of example 1, which indicates that the raw material ratios of examples 1-5 are favorable for preparing the cleaning-resistant polyurethane foam materials with better hydrophobicity, toughness and elasticity.

Combining example 5 and comparative examples 4-6, and combining Table six, it can be seen that the foam samples of comparative examples 4-6 have significantly reduced static contact angles, tensile strengths, and percent rebound compared to the foam sample of example 5, indicating that the presence of the mercapto-modified soy oil polyol, the alkenyl-containing silane, and the photoinitiator contributes to improved hydrophobicity, toughness, and elasticity of the polyurethane foam.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.