1. A composition of PVC plastic fluorescent whitening agent comprises the following operation steps:

75-95 parts of fluorescent whitening agent, 5-25 parts of dispersant and 0.01-0.1 part of blue-phase permanent violet RL are fully and uniformly stirred according to the mass parts to form the fluorescent whitening agent composition for PVC plastics.

2. The composition of PVC plastic fluorescent whitening agent according to claim 1, characterized in that: the brightener for the PVC plastic is one of a fluorescent brightener OB or a fluorescent brightener OB-1.

3. The composition of PVC plastic fluorescent whitening agent according to claim 1, characterized in that: the polymer dispersant is prepared by adopting the following method, and comprises the following steps:

adding 20-31 parts by mass of a silane coupling agent, 16-22 parts by mass of diallylamine hydrochloride, 300 parts by mass of white oil 200 and 5 parts by mass of an organic base into a reaction kettle, introducing nitrogen, and then, under the stirring condition, controlling the temperature to be 60-78 ℃ and preserving the heat for 3-4 hours; then adding 5-9 parts of vinyl glycol monoether and 1.2-3.5 parts of initiator, controlling the temperature to be 60-75 ℃, and preserving the heat for 1-3 hours; and finally, cooling, filtering and drying to obtain the high molecular dispersing agent.

4. A method for producing a polymeric dispersant according to claim 3, characterized in that: the silane coupling agent is one of 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

5. A method for producing a polymeric dispersant according to claim 3, characterized in that: the organic alkali is one of ethanolamine, sodium ethoxide, sodium methoxide, triethylamine, piperidine or pyridine.

6. A method for producing a polymeric dispersant according to claim 3, characterized in that: the organic base is preferably one of sodium ethoxide, sodium methoxide and triethylamine.

7. A method for producing a polymeric dispersant according to claim 3, characterized in that: the initiator is benzoyl peroxide.

8. The composition of PVC plastic fluorescent whitening agent according to claim 1, characterized in that: the preferential specific surface area of the blue phase permanent violet RL is 60-120m²/g。

Background

The fluorescent whitening agent for PVC plastics can better increase the whiteness, brightness and weather resistance of the product appearance, increase the surface hardness and tensile strength, so that plastic products formed at high temperature such as injection molding, extrusion molding and the like are corrosion-resistant, firm and durable, and have longer service life.

The fluorescent whitening agent for PVC plastics belongs to optical whitening, absorbs near ultraviolet light invisible to naked eyes of people, emits blue fluorescence visible to the naked eyes of people, gives visual organs with increased whiteness feeling by utilizing the fluorescence, does not cause damage to plastic products, and is the most effective and commonly used method for improving the whiteness of PVC plastic products at present. The temperature of most plastic manufacturing processes is high, some of the plastic manufacturing processes even reach more than 300 ℃, and only the fluorescent whitening agent OB-1 can bear the high temperature of 350 ℃. In the face of high temperatures above 300 ℃, other whitening agents are only impressive. The following are the temperature tolerance limits of common plastic optical brighteners: OB-1: 350 ℃; KCB: 215 ℃ of water; KSN: 275 ℃; 127: at 220 ℃.

The fluorescent whitening agent OB-1, 2,2- (4, 4-distyryl) dibenzoxazole is a yellow crystal, has the melting point of 359-. The fluorescent whitening agent OB-1 is a high-efficiency fluorescent whitening agent, is widely used for plastics such as ABS, PS, HIPS, PC, PP, PE, EVA, hard PVC and the like, and has the characteristics of excellent whitening effect, excellent thermal stability, very small addition amount and the like.

CN201310529198.8 discloses a tetrasulfonic acid amphoteric fluorescent whitening agent and a preparation method thereof, and mainly solves the technical problems of narrow application range and poor water solubility of solid dosage forms of the existing fluorescent whitening agent. The technical scheme adopted by the invention is that the tetrasulfonic acid amphoteric fluorescent whitening agent mainly comprises one or more compounds, and the tetrasulfonic acid amphoteric fluorescent whitening agent comprises cyanuric chloride, p-diethanol amidobenzene sulfonic acid, 4' -diaminostilbene-disulfonic acid and tertiary amine compounds in the mass ratio of: 1:1:0.5:1.2, adding cyanuric chloride and p-diethanolamino benzenesulfonic acid into ice water for reaction, adding a sodium salt solution of 4, 4' -diaminostilbene-disulfonic acid into the reaction solution, adding a tertiary amine compound into the reaction solution for reaction, desalting, and adding an auxiliary agent to obtain a liquid product. And carrying out pressure spray drying on the liquid product to obtain a solid product. The fluorescent whitening agent prepared by the invention can be applied under neutral, alkaline and acidic conditions, and does not pollute the environment when in use.

CN201410318542.3 discloses a PVC pipe and a method for preparing the same. The method comprises the steps of extruding and molding PVC resin, a stabilizer, CPE (chlorinated polyethylene), EPR (ethylene propylene rubber), stearic acid, a filler, paraffin, an OB fluorescent whitening agent and PE wax into the PVC pipe; wherein the average polymerization degree of the PVC resin is 720-850; the weight average molecular weight of the PE wax is 2000-5000; the weight average molecular weight of the CPE is 10-30 ten thousand, and the content of chlorine in the CPE is 25-45 parts by weight relative to 100 parts by weight of the CPE; the weight average molecular weight of the EPR is 20-40 ten thousand; the stabilizer is one or more of calcium stearate, calcium ricinoleate, zinc stearate and zinc ricinoleate; the filler is calcium carbonate and/or titanium dioxide. The PVC pipe has excellent impact resistance.

CN200910075377.2 discloses a preparation method of a stilbene triazine liquid fluorescent whitening agent composition, which provides a preparation method of symmetrical and asymmetrical stilbene triazine liquid fluorescent whitening agent compositions, cyanuric chloride, sulfanilic acid, 4-diaminostilbene-2, 2-disulfonic acid, morpholine and diethanolamine are used as raw materials, the compositions are synthesized by three-step reaction, and the compositions are obtained by adopting a nanofiltration membrane filtering method for desalination and filtration treatment: . The liquid fluorescent whitening agent composition prepared by the invention has a compounding synergistic effect, has a better whitening effect than that of a single component, and the method not only can improve the quality of the fluorescent whitening agent, but also can reduce the consumption of a large amount of raw materials, so that the yield and the quality of the product are greatly improved.

The fluorescent whitening agent used in the above invention and the prior patent is unstable, for example, the fluorescent whitening effect of the fluorescent whitening agent 127 is reduced rapidly in outdoor environment, and the whitening effect is only 40% after 20 days, so further research and improvement are needed. In addition, the optimum amount of optical brightener OB-1 depends on its compatibility with the polymer, and too high an amount of brightener causes incompatibility and migration.

Disclosure of Invention

The invention provides a method for preparing a composition of a PVC plastic fluorescent brightener, aiming at the problems of instability of the fluorescent brightener generated in the existing production process of adding the fluorescent brightener into PVC plastic and the compatibility between the fluorescent brightener OB-1 and a polymer.

A composition of PVC plastic fluorescent whitening agent comprises the following operation steps:

75-95 parts of fluorescent whitening agent, 5-25 parts of dispersant and 0.01-0.1 part of blue-phase permanent violet RL are fully and uniformly stirred according to the mass parts to form the fluorescent whitening agent composition for PVC plastics.

Further, the whitening agent for PVC plastics is one of a fluorescent whitening agent OB or a fluorescent whitening agent OB-1;

further, the polymer dispersant is prepared by adopting the following method, and comprises the following steps:

adding 20-31 parts by mass of a silane coupling agent, 16-22 parts by mass of diallylamine hydrochloride, 300 parts by mass of white oil 200 and 5 parts by mass of an organic base into a reaction kettle, introducing nitrogen, and then, under the stirring condition, controlling the temperature to be 60-78 ℃ and preserving the heat for 3-4 hours; then adding 5-9 parts of vinyl glycol monoether and 1.2-3.5 parts of initiator, controlling the temperature to be 60-75 ℃, and preserving the heat for 1-3 hours; and finally, cooling, filtering and drying to obtain the high molecular dispersing agent.

Further, the silane coupling agent is one of 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane;

further, the organic base is one of ethanolamine, sodium ethoxide, sodium methoxide, triethylamine, piperidine or pyridine;

further, the organic base is preferably one of sodium ethoxide, sodium methoxide and triethylamine;

further, the initiator is benzoyl peroxide;

further, the preferential specific surface area of the blue phase permanent violet RL is 60-120m 2/g.

The reaction mechanism is as follows:

the dispersant prepared by the invention adopts 3-mercaptopropyltrimethoxysilane and diallylamine hydrochloride to carry out Michael addition reaction, and then carries out emulsion polymerization with vinyl glycol monoether, and the main chain and part of branched chains, such as oxysilane, have better hydrophobicity and can be better adsorbed with a fluorescent whitening agent OB-1 in the action modes of hydrogen bond adsorption and the like; the branched chain of the dispersant enables the fluorescent whitening agent particles to be well dispersed in the water solution;

the technical effects are as follows:

(1) the invention has high whiteness value of PVC plastics, the whiteness value can be improved by more than 5, and the amount of the fluorescent whitening agent OB-1 is less than 5 parts to reach the same whiteness value.

(2) Adding a certain proportion of fluorescent whitening agent, matching with dispersant and blue permanent violet RL, controlling the proportion of the fluorescent whitening agent, and improving the whiteness of the PVC plastic, thereby improving the covering property of the calendered film.

Drawings

FIG. 1 is a photograph of the PVC plastic fluorescent whitening agent printed plate in Table 1. A is light yellow, B and C are white.

FIG. 2 is a Fourier infrared spectrum of the polymeric dispersant prepared in example 2;

the telescopic absorption peak of the carbon-hydrogen bond exists near 2949/2839cm < -1 >, the telescopic absorption peak of the carbon-nitrogen single bond exists near 1331cm < -1 >, and the telescopic absorption peak of the nitrogen-hydrogen bond exists near 3401cm < -1 >, which indicates that the diallyl amine hydrochloride participates in the reaction; the stretching absorption peak of silicon-carbon bond exists near 650cm < -1 >, and the antisymmetric stretching absorption peak of silicon-oxygen bond exists near 1078cm < -1 >, which indicates that the silane coupling agent participates in the reaction; an antisymmetric telescopic absorption peak of ether bond exists near 1113cm-1, which indicates that the vinyl glycol monoether participates in the reaction.

Detailed Description

The invention is further illustrated by the following specific examples:

A. preparing a sample:

adding 40mgPVC plastic fluorescent brightener into 200g PVC plastic base material (without brightener), mixing the two materials uniformly, and injection molding by a plastic injection molding machine to obtain the plastic plate.

The blank sample is a PVC plastic base material (without whitening agent) provided for Huajia plastic industry, the whitening agent is not added, and the whiteness is 52.66 percent;

B. test standards and methods:

the aging whiteness of the PVC plastic plate obtained in the examples 1-5 and the comparative examples 1-3 is tested according to the oven aging resistance test in GB/T15595-2008, and the test results are shown in Table 1.

Example 1

A composition of PVC plastic fluorescent whitening agent comprises the following operation steps:

a fluorescent whitening agent composition for PVC plastics comprises the following components: and fully and uniformly stirring 75g of fluorescent brightener, 5g of dispersant and 0.01g of blue phase permanent violet RL to form the fluorescent brightener composition for PVC plastics.

Further, the brightener for PVC plastics is a fluorescent brightener OB;

further, the polymer dispersant is prepared by adopting the following method, and comprises the following steps:

adding 20g of silane coupling agent, 16g of diallyl amine hydrochloride, 200g of white oil and 3g of organic base into a reaction kettle, introducing nitrogen, controlling the temperature to be 65 ℃ under the stirring condition, and preserving the temperature for 3 hours; then adding 5g of vinyl glycol monoether and 1.2g of initiator, controlling the temperature to 65 ℃, and preserving the heat for 2 hours; and finally, cooling, filtering and drying to obtain the high molecular dispersing agent.

Further, the silane coupling agent is 3-mercaptopropyltrimethoxysilane;

further, the organic base is ethanolamine;

further, the initiator is benzoyl peroxide;

further, the specific surface area of the blue phase permanent violet RL is 100m²/g。

Example 2

A composition of PVC plastic fluorescent whitening agent comprises the following operation steps:

a fluorescent whitening agent composition for PVC plastics comprises the following components: 80g of fluorescent whitening agent, 10g of dispersant and 0.03g of blue-phase permanent violet RL are fully and uniformly stirred to form the fluorescent whitening agent composition for PVC plastics.

Further, the brightener for PVC plastics is a fluorescent brightener OB;

further, the polymer dispersant is prepared by adopting the following method, and comprises the following steps:

adding 24g of silane coupling agent, 18g of diallyl amine hydrochloride, 240g of white oil and 3g of organic base into a reaction kettle, introducing nitrogen, and then keeping the temperature at 70 ℃ for 4 hours under the stirring condition; then adding 6g of vinyl glycol monoether and 1.5g of initiator, controlling the temperature to be 70 ℃, and preserving the heat for 2 hours; and finally, cooling, filtering and drying to obtain the high molecular dispersing agent.

Further, the silane coupling agent is 3-mercaptopropyltrimethoxysilane;

further, the organic base is piperidine;

further, the initiator is benzoyl peroxide;

further, the specific surface area of the blue phase permanent violet RL is 100m²/g。

Example 3

A composition of PVC plastic fluorescent whitening agent comprises the following operation steps:

a fluorescent whitening agent composition for PVC plastics comprises the following components: 85g of fluorescent whitening agent, 15g of dispersant and 0.06g of blue-phase permanent violet RL are fully and uniformly stirred to form the fluorescent whitening agent composition for PVC plastics.

Further, the brightener for PVC plastics is a fluorescent brightener OB-1;

further, the polymer dispersant is prepared by adopting the following method, and comprises the following steps:

adding 26g of silane coupling agent, 20g of diallyl amine hydrochloride, 260g of white oil and 4g of organic base into a reaction kettle, introducing nitrogen, controlling the temperature to be 75 ℃ under the stirring condition, and preserving the temperature for 4 hours; then adding 6g of vinyl glycol monoether and 2.4g of initiator, controlling the temperature to be 70 ℃, and preserving the heat for 2 hours; and finally, cooling, filtering and drying to obtain the high molecular dispersing agent.

Further, the silane coupling agent is 3-mercaptopropyltriethoxysilane;

further, the organic base is sodium ethoxide;

further, the initiator is benzoyl peroxide;

further, the specific surface area of the blue phase permanent violet RL is 100m²/g。

Example 4

A composition of PVC plastic fluorescent whitening agent comprises the following operation steps:

a fluorescent whitening agent composition for PVC plastics comprises the following components: and fully and uniformly stirring 90g of fluorescent brightener, 20g of dispersant and 0.08g of blue phase permanent violet RL to form the fluorescent brightener composition for PVC plastics.

Further, the brightener for PVC plastics is a fluorescent brightener OB-1;

further, the polymer dispersant is prepared by adopting the following method, and comprises the following steps:

adding 28g of silane coupling agent, 20g of diallyl amine hydrochloride, 280g of white oil and 4g of organic base into a reaction kettle, introducing nitrogen, controlling the temperature to be 75 ℃ under the stirring condition, and preserving the temperature for 4 hours; then adding 8g of vinyl glycol monoether and 3g of initiator, controlling the temperature to be 70 ℃, and preserving the heat for 2 hours; and finally, cooling, filtering and drying to obtain the high molecular dispersing agent.

Further, the silane coupling agent is 3-mercaptopropyltriethoxysilane;

further, the organic base is sodium methoxide;

further, the initiator is benzoyl peroxide;

further, the specific surface area of the blue phase permanent violet RL is 100m²/g。

Example 5

A composition of PVC plastic fluorescent whitening agent comprises the following operation steps:

a fluorescent whitening agent composition for PVC plastics comprises the following components: 95g of fluorescent whitening agent, 25g of dispersant and 0.1g of blue-phase permanent violet RL are fully and uniformly stirred to form the fluorescent whitening agent composition for PVC plastics.

Further, the brightener for PVC plastics is a fluorescent brightener OB-1;

further, the polymer dispersant is prepared by adopting the following method, and comprises the following steps:

adding 31g of silane coupling agent, 22g of diallyl amine hydrochloride, 300g of white oil and 5g of organic base into a reaction kettle, introducing nitrogen, controlling the temperature to be 70 ℃ under the stirring condition, and preserving the temperature for 4 hours; then adding 9g of vinyl glycol monoether and 3.5g of initiator, controlling the temperature to be 70 ℃, and preserving the heat for 2 hours; and finally, cooling, filtering and drying to obtain the high molecular dispersing agent.

Further, the silane coupling agent is 3-mercaptopropyltriethoxysilane;

further, the organic base is triethylamine;

further, the initiator is benzoyl peroxide;

further, the specific surface area of the blue phase permanent violet RL is 100m²/g。

Comparative example 1

A composition of PVC plastic fluorescent whitening agent comprises the following operation steps:

a fluorescent whitening agent composition for PVC plastics comprises the following components: 80g of fluorescent whitening agent and 0.05g of blue phase permanent violet RL are fully and uniformly stirred to form the fluorescent whitening agent composition for PVC plastics.

Further, the brightener for PVC plastics is a fluorescent brightener OB;

further, the preferential specific surface area of the blue phase permanent violet RL is 60-120m 2/g.

Comparative example 2

A composition of PVC plastic fluorescent whitening agent comprises the following operation steps:

a fluorescent whitening agent composition for PVC plastics comprises the following components: 85g of fluorescent whitening agent, 20g of light calcium carbonate and 0.08g of blue phase permanent violet RL are fully and uniformly stirred to form the fluorescent whitening agent composition for PVC plastics.

Further, the brightener for PVC plastics is a fluorescent brightener OB-1;

further, the specific surface area of the blue phase permanent violet RL is 100m²/g。

Comparative example 3

A composition of PVC plastic fluorescent whitening agent comprises the following operation steps:

a fluorescent whitening agent composition for PVC plastics comprises the following components: 85g of fluorescent whitening agent and 20g of dispersant are sufficiently stirred uniformly to form the fluorescent whitening agent composition for PVC plastics.

Further, the brightener for PVC plastics is a fluorescent brightener OB;

further, the polymer dispersant is prepared by adopting the following method, and comprises the following steps:

adding 24g of silane coupling agent, 20g of diallyl amine hydrochloride, 280g of white oil and 4g of organic base into a reaction kettle, introducing nitrogen, controlling the temperature to be 75 ℃ under the stirring condition, and preserving the temperature for 4 hours; then adding 8g of vinyl glycol monoether and 3g of initiator, controlling the temperature to be 70 ℃, and preserving the heat for 3 hours; and finally, cooling, filtering and drying to obtain the high molecular dispersing agent.

Further, the silane coupling agent is 3-mercaptopropyltriethoxysilane;

further, the organic base is sodium methoxide;

further, the initiator is benzoyl peroxide;

further, the preferential specific surface area of the blue phase permanent violet RL is 100m 2/g.

Table 1, examples and comparative examples the results of the whiteness performance test on PVC plastics with addition of fluorescent whitening agent compositions

As can be seen from Table 1, the composition added with the PVC plastic fluorescent whitening agent in the preferred embodiments 1-5 of the present application is added into a resin system during polymerization, which significantly improves the static aging whiteness (160 ℃, 10 min) of the finished resin, and is a method for synthesizing high-quality PVC resin.

Further, the influence of the addition of the fluorescent whitening agent in the PVC plastic on the whitening effect is detected,

reagent and sample

A- -PVC plastic base material, provided by Yingrun industry and trade Co., Ltd, of Jiangshan city;

B-PVC plastic fluorescent whitening agent, containing 100% of fluorescent whitening agent;

the C-PVC plastic fluorescent whitening agent composition is prepared by adopting the formula of the invention, and contains 95% of fluorescent whitening agent, 4.985% of dispersing agent and 0.015% of blue-phase permanent violet RL.

Instrumentation and equipment

South China plastic machine, model: NT-50T;

a rolling machine, self-made;

precision electronic balance ACCULAB, model: ALC-210, d =0.1 mg;

full-automatic whiteness meter, beijing cong optical instruments ltd, model: WSD-3.

Detection step

1 beating plate

Weighing 200g of PVC plastic base material, filling into a 500ml plastic bottle, adding 0.04 g of PVC plastic fluorescent whitening agent, covering the bottle cap tightly, rolling and mixing in a rolling machine for 20 minutes, and striking a plate by using a Nantian plastic machine at 190 ℃.

2 whiteness detection

The whiteness of the plate sample was measured with a full-automatic whiteness meter.

TABLE 2 whiteness detection results of PVC plastic fluorescent whitening agent striking plate

Sample (I)	Brightness of light	Red green value	Yellow-blue value	Whiteness degree	Coefficient of hue	Remarks for note
							A	90.29	0.10	5.13	52.66	-2.20	Without whitening agent
A+B	91.64	4.18	-2.07	93.61	-6.21	Adding 0.02% of B whitening agent
							A+C	92.66	2.91	-2.24	94.10	-2.16	Adding 0.02% of C whitening agent

FIG. 1 is a photograph of a PVC plastic fluorescent whitening agent printed plate

The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.