CN115340638A - Preparation method of transparent impact modifier for polyvinyl chloride - Google Patents
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- CN115340638A CN115340638A CN202211269673.8A CN202211269673A CN115340638A CN 115340638 A CN115340638 A CN 115340638A CN 202211269673 A CN202211269673 A CN 202211269673A CN 115340638 A CN115340638 A CN 115340638A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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Abstract
The invention discloses a preparation method of a transparent impact modifier for polyvinyl chloride, belonging to the technical field of impact modifiers, and the preparation method comprises the following steps: preparing seed emulsion, preparing elastomer, preparing core-shell graft copolymer, and post-treating; adding deionized water, styrene, propyl methacrylate, sodium persulfate, sodium dodecyl benzene sulfonate and dispersion into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.07-0.08MPa, then filling nitrogen into the closed reaction container until the pressure is 0.14-0.16MPa, starting stirring, and stirring to obtain seed emulsion; the prepared transparent impact modifier for polyvinyl chloride can improve the impact resistance, haze, transparency and strength of the acrylate impact modifier, and ensure that the fracture toughness and high temperature resistance of polyvinyl chloride are not reduced while the impact resistance at low temperature is improved.
Description
Technical Field
The invention relates to the technical field of impact modifiers, in particular to a preparation method of a transparent impact modifier for polyvinyl chloride.
Background
The impact modifier is a chemical product capable of improving low-temperature embrittlement of a high polymer material and endowing the high polymer material with higher toughness, and the main varieties are chlorinated polyethylene, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, acrylate copolymer and the like.
The polyvinyl chloride resin has poor processing and forming performance, and the impact strength of a processed and formed product is poor, particularly the impact strength of a transparent product is worse, and an impact modifier needs to be added, but among the current common impact modifiers, the transparency of chlorinated polyethylene is poor, the ultraviolet resistance of methyl methacrylate-butadiene-styrene copolymer is poor, the heat resistance of acrylonitrile-butadiene-styrene copolymer and ethylene-vinyl acetate copolymer is poor, the impact resistance of acrylate copolymer and the impact resistance at low temperature are poor, and the compatibility with polyvinyl chloride is poor, so that the strength of the polyvinyl chloride is influenced.
In order to solve the above problems, the most common method at present is to prepare the acrylate impact modifier with a core-shell structure, but the acrylate impact modifier with a core-shell structure has low haze and poor transparency, and in order to solve the problems, the most common method at present is to prepare the acrylate impact modifier with a hard-soft-hard structure, which can well solve the problems of insufficient impact resistance, low haze and poor transparency of the acrylate impact modifier, and can also improve the strength and impact resistance at low temperature of the acrylate impact modifier, but the prepared acrylate impact modifier can reduce the fracture toughness of polyvinyl chloride and can also reduce the high temperature resistance of polyvinyl chloride. Therefore, the research and development of a method for preparing a transparent impact modifier for polyvinyl chloride, which can improve the impact resistance, haze, transparency and strength of acrylate impact modifiers and ensure that the fracture toughness and high temperature resistance of polyvinyl chloride are not reduced while the impact resistance at low temperature is improved, are technical problems to be solved urgently at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a transparent impact modifier for polyvinyl chloride, which can improve the impact resistance, haze, transparency and strength of the acrylate impact modifier, and ensure that the fracture toughness and high temperature resistance of the polyvinyl chloride are not reduced while the impact resistance at low temperature is improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing a transparent impact modifier for polyvinyl chloride comprises the following steps: preparing seed emulsion, preparing elastomer, preparing core-shell graft copolymer and post-treating.
Adding deionized water, styrene, propyl methacrylate, sodium persulfate, sodium dodecyl benzene sulfonate and dispersion into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.07-0.08MPa, then filling nitrogen into the closed reaction container until the pressure is 0.14-0.16MPa, starting stirring, controlling the stirring speed to 150-180rpm, and stirring for 1.5-1.8h to obtain seed emulsion;
in the preparation of the seed emulsion, the weight ratio of deionized water, styrene, propyl methacrylate, potassium persulfate, sodium dodecyl benzene sulfonate to the dispersion is (100-105);
adding deionized water and pregelatinized starch into a reaction vessel, heating to 50-55 ℃, starting stirring, controlling the stirring speed to 100-120rpm, then adding a sodium hydroxide aqueous solution with the mass concentration of 28-30%, stirring for reacting for 35-40min, heating to 80-85 ℃, adding potassium persulfate, continuing to stir for 20-25min, adding sodium bisulfite, continuing to stir for 10-12min, then adding sodium tripolyphosphate, and continuing to stir for 10-12min to obtain a dispersion liquid;
in the preparation of the dispersion, the weight ratio of deionized water, pregelatinized starch, 28-30% sodium hydroxide aqueous solution, potassium persulfate, sodium bisulfite and sodium tripolyphosphate is (400-420);
the number average particle size of the seed emulsion is 80-90nm.
Adding deionized water, seed emulsion, methyl acrylate, allyl methacrylate, sodium persulfate and sodium dodecyl benzene sulfonate into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.08-0.085MPa, then filling nitrogen into the closed reaction container until the pressure is 0.13-0.15MPa, starting stirring, controlling the stirring speed to 200-220rpm, and stirring for 2.5-3 hours to obtain elastomer latex;
in the preparation of the elastomer, the weight ratio of deionized water, the seed emulsion, the methyl acrylate, the allyl methacrylate, the sodium persulfate and the sodium dodecyl benzene sulfonate is (100-105);
the number average particle size of the elastomer latex is 90-100nm.
Adding elastomer latex, deionized water, butyl methacrylate, sodium persulfate and sodium dodecyl benzene sulfonate into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.08-0.085MPa, then filling nitrogen into the closed reaction container until the pressure is 0.12-0.14MPa, then starting stirring, controlling the stirring speed to 200-220rpm, stirring for 1-1.5h, continuing to fill nitrogen until the pressure is 0.15-0.17MPa, and continuing to stir for 1-1.5h to obtain a graft copolymer emulsion;
in the preparation of the core-shell graft copolymer, the weight ratio of elastomer latex, deionized water, butyl methacrylate, sodium persulfate and sodium dodecyl benzene sulfonate is 190-200;
the number average particle size of the graft copolymer emulsion is 90-100nm.
The post-treatment comprises the steps of adding a graft copolymer emulsion, formaldehyde and a sodium hydroxide aqueous solution with the mass concentration of 28-30% into a reaction container, heating the temperature to 50-55 ℃, starting stirring, controlling the stirring speed to 200-220rpm, stirring for 15-18min, adding dimethylamine, continuing stirring for 18-20min, then adding a hydrochloric acid aqueous solution with the mass concentration of 18-20%, continuing stirring for 10-12min to obtain a cationized graft copolymer emulsion, carrying out spray drying on the cationized graft copolymer emulsion, controlling the inlet temperature in the spray drying to be 120-130 ℃, controlling the outlet temperature to be 60-70 ℃, and finishing the spray drying to obtain a transparent impact modifier;
in the post-treatment, the weight ratio of the graft copolymer emulsion to formaldehyde to 28-30% aqueous sodium hydroxide solution to dimethylamine to 18-20% aqueous hydrochloric acid is 400-410-7-12.
Compared with the prior art, the invention has the following beneficial effects:
(1) The transparent impact modifier for polyvinyl chloride prepared by the invention can improve the impact resistance of polyvinyl chloride at normal temperature by cationizing the graft copolymer emulsion in the preparation process, and the notch impact strength of the polyvinyl chloride added with the transparent impact modifier prepared by the invention at 25 ℃ is 16.4-17.5kJ/m 2 ；
(2) The transparent impact modifier for polyvinyl chloride prepared by the invention can improve the transparency of polyvinyl chloride at normal temperature by adding the dispersion liquid into the prepared seed emulsion, and the polyvinyl chloride added with the transparent impact modifier has the haze of 6.2-6.7% and the light transmittance of 90.4-92.7%;
(3) The transparent impact modifier for polyvinyl chloride prepared by the invention can improve the strength of polyvinyl chloride by cationizing the graft copolymer emulsion in the preparation, and the polyvinyl chloride added with the transparent impact modifier has the tensile strength of 55.8-56.7MPa and the bending strength of 94.2-95.9MPa;
(4) The transparent impact modifier for polyvinyl chloride prepared by the invention can improve the impact resistance of polyvinyl chloride at low temperature by cationizing the graft copolymer emulsion in the preparation, and the notch impact strength of the polyvinyl chloride added with the transparent impact modifier prepared by the invention at-15 ℃ is 16.2-17.4kJ/m 2 ；
(5) The transparent impact modifier for polyvinyl chloride prepared by the invention can improve the fracture toughness of polyvinyl chloride by cationizing the graft copolymer emulsion in the preparation process, and the elongation at break of the polyvinyl chloride added with the transparent impact modifier prepared by the invention is 341-357 percent;
(6) The transparent impact modifier for polyvinyl chloride prepared by the invention can improve the high temperature resistance of polyvinyl chloride by adding dispersion liquid into the prepared seed emulsion and cationizing the graft copolymer emulsion in the preparation process, and after the polyvinyl chloride added with the transparent impact modifier prepared by the invention is placed at 55 ℃ and stands for 100 days, the notch impact strength at 25 ℃ is 16.2-17.2kJ/m 2 The haze is 6.1-6.5%, the light transmittance is 90.1-92.4%, the tensile strength is 55.7-56.4MPa, and the bending strength is 94.0-95.7MPa.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A method for preparing transparent impact modifier for polyvinyl chloride comprises the following steps:
1. preparing a seed emulsion: adding deionized water, styrene, propyl methacrylate, sodium persulfate, sodium dodecyl benzene sulfonate and dispersion into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.07MPa, then filling nitrogen into the closed reaction container until the pressure is 0.14MPa, then starting stirring, controlling the stirring speed to 150rpm, and stirring for 1.5 hours to obtain a seed emulsion;
wherein, the weight ratio of the deionized water, the styrene, the propyl methacrylate, the potassium persulfate, the sodium dodecyl benzene sulfonate and the dispersion liquid is 100;
the preparation method of the dispersion comprises the following steps: adding deionized water and pregelatinized starch into a reaction vessel, heating to 50 ℃, starting stirring, controlling the stirring speed to 100rpm, then adding a 28% sodium hydroxide aqueous solution, stirring for reacting for 35min, heating to 80 ℃, adding potassium persulfate, continuing stirring for 20min, adding sodium bisulfite, continuing stirring for 10min, then adding sodium tripolyphosphate, and continuing stirring for 10min to obtain a dispersion liquid;
wherein the weight ratio of deionized water, pregelatinized starch, 28% sodium hydroxide aqueous solution, potassium persulfate, sodium bisulfite and sodium tripolyphosphate is (400);
the number average particle size of the seed emulsion is 80nm.
2. Preparing an elastomer: adding deionized water, seed emulsion, methyl acrylate, allyl methacrylate, sodium persulfate and sodium dodecyl benzene sulfonate into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.08MPa, then filling nitrogen into the closed reaction container until the pressure is 0.13MPa, then starting stirring, controlling the stirring speed to 200rpm, and stirring for 2.5 hours to obtain elastomer latex;
wherein the weight ratio of the deionized water to the seed emulsion to the methyl acrylate to the allyl methacrylate to the sodium persulfate to the sodium dodecylbenzenesulfonate is 100;
the number average particle diameter of the elastomer latex is 90nm.
3. Preparation of core-shell graft copolymers: adding elastomer latex, deionized water, butyl methacrylate, sodium persulfate and sodium dodecyl benzene sulfonate into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.08MPa, then filling nitrogen into the closed reaction container until the pressure is 0.12MPa, then starting stirring, controlling the stirring speed to 200rpm, stirring for 1h, continuously filling nitrogen until the pressure is 0.15MPa, and continuously stirring for 1h to obtain a graft copolymer emulsion;
wherein the weight ratio of the elastomer latex to the deionized water to the butyl methacrylate to the sodium persulfate to the sodium dodecylbenzenesulfonate is 190.08;
the number average particle size of the graft copolymer emulsion was 90nm.
4. And (3) post-treatment: adding the graft copolymer emulsion, formaldehyde and a sodium hydroxide aqueous solution with the mass concentration of 28% into a reaction container, heating the temperature to 50 ℃, starting stirring, controlling the stirring speed to 200rpm, stirring for 15min, adding dimethylamine, continuing stirring for 18min, then adding a hydrochloric acid aqueous solution with the mass concentration of 18%, continuing stirring for 10min to obtain a cationized graft copolymer emulsion, performing spray drying on the cationized graft copolymer emulsion, controlling the inlet temperature in the spray drying to be 120 ℃, controlling the outlet temperature to be 60 ℃, and finishing the spray drying to obtain a transparent impact modifier;
wherein, the weight ratio of the graft copolymer emulsion to formaldehyde to 28% by mass of sodium hydroxide aqueous solution to dimethylamine to 18% by mass of hydrochloric acid aqueous solution is 400.
Example 2
A preparation method of a transparent impact modifier for polyvinyl chloride comprises the following steps:
1. preparing a seed emulsion: adding deionized water, styrene, propyl methacrylate, sodium persulfate, sodium dodecyl benzene sulfonate and dispersion into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.075MPa, then filling nitrogen into the closed reaction container until the pressure is 0.15MPa, then starting stirring, controlling the stirring speed to 160rpm, and stirring for 1.6h to obtain seed emulsion;
wherein, the weight ratio of the deionized water, the styrene, the propyl methacrylate, the potassium persulfate, the sodium dodecyl benzene sulfonate and the dispersion liquid is 102.41;
the preparation method of the dispersion comprises the following steps: adding deionized water and pregelatinized starch into a reaction vessel, heating to 52 ℃, starting stirring, controlling the stirring speed to 110rpm, then adding a 29% sodium hydroxide aqueous solution, stirring for reacting for 37min, heating to 82 ℃, adding potassium persulfate, continuing stirring for 22min, adding sodium bisulfite, continuing stirring for 11min, then adding sodium tripolyphosphate, and continuing stirring for 11min to obtain a dispersion liquid;
wherein the weight ratio of deionized water, pregelatinized starch, 29% sodium hydroxide aqueous solution, potassium persulfate, sodium bisulfite and sodium tripolyphosphate is 410.1;
the number average particle size of the seed emulsion is 85nm.
2. Preparing an elastomer: adding deionized water, seed emulsion, methyl acrylate, allyl methacrylate, sodium persulfate and sodium dodecyl benzene sulfonate into a closed reaction container, vacuumizing the closed reaction container to the vacuum degree of 0.082MPa, then filling nitrogen into the closed reaction container to the pressure of 0.14MPa, then starting stirring, controlling the stirring speed to 210rpm, and stirring for 2.7 hours to obtain elastomer latex;
wherein the weight ratio of the deionized water to the seed emulsion to the methyl acrylate to the allyl methacrylate to the sodium persulfate to the sodium dodecylbenzenesulfonate is 102;
the number average particle diameter of the elastomer latex is 95nm.
3. Preparation of core-shell graft copolymers: adding elastomer latex, deionized water, butyl methacrylate, sodium persulfate and sodium dodecyl benzene sulfonate into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.082MPa, then filling nitrogen into the closed reaction container until the pressure is 0.13MPa, then starting stirring, controlling the stirring speed to 210rpm, stirring for 1.2h, then continuously filling nitrogen until the pressure is 0.16MPa, and continuously stirring for 1.2h to obtain a graft copolymer emulsion;
wherein the weight ratio of the elastomer latex to the deionized water to the butyl methacrylate to the sodium persulfate to the sodium dodecylbenzenesulfonate is 195.09;
the number average particle size of the graft copolymer emulsion was 95nm.
4. And (3) post-treatment: adding the graft copolymer emulsion, formaldehyde and 29% sodium hydroxide aqueous solution into a reaction container, heating the temperature to 52 ℃, starting stirring, controlling the stirring speed to 210rpm, stirring for 17min, adding dimethylamine, continuing stirring for 19min, then adding 19% hydrochloric acid aqueous solution, continuing stirring for 11min to obtain cationized graft copolymer emulsion, carrying out spray drying on the cationized graft copolymer emulsion, controlling the inlet temperature in the spray drying to 125 ℃, controlling the outlet temperature to 65 ℃, and finishing the spray drying to obtain the transparent impact modifier;
wherein, the weight ratio of the graft copolymer emulsion to formaldehyde to 29% by mass of aqueous sodium hydroxide solution to dimethylamine to 19% by mass of aqueous hydrochloric acid solution is 405.
Example 3
A preparation method of a transparent impact modifier for polyvinyl chloride comprises the following steps:
1. preparing a seed emulsion: adding deionized water, styrene, propyl methacrylate, sodium persulfate, sodium dodecyl benzene sulfonate and dispersion into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.08MPa, then filling nitrogen into the closed reaction container until the pressure is 0.16MPa, then starting stirring, controlling the stirring speed to 180rpm, and stirring for 1.8 hours to obtain a seed emulsion;
wherein, the weight ratio of the deionized water, the styrene, the propyl methacrylate, the potassium persulfate, the sodium dodecyl benzene sulfonate and the dispersion liquid is 105.8;
the preparation method of the dispersion comprises the following steps: adding deionized water and pregelatinized starch into a reaction vessel, heating to 55 ℃, starting stirring, controlling the stirring speed to 120rpm, then adding a sodium hydroxide aqueous solution with the mass concentration of 30%, stirring for reacting for 40min, then heating to 85 ℃, adding potassium persulfate, continuing stirring for 25min, adding sodium bisulfite, continuing stirring for 12min, then adding sodium tripolyphosphate, and continuing stirring for 12min to obtain a dispersion liquid;
wherein, the weight ratio of deionized water, pregelatinized starch, 30% sodium hydroxide aqueous solution, potassium persulfate, sodium bisulfite and sodium tripolyphosphate is 420;
the number average particle size of the seed emulsion is 90nm.
2. Preparing an elastomer: adding deionized water, seed emulsion, methyl acrylate, allyl methacrylate, sodium persulfate and sodium dodecyl benzene sulfonate into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.085MPa, then filling nitrogen into the closed reaction container until the pressure is 0.15MPa, then starting stirring, controlling the stirring speed to 220rpm, and stirring for 3 hours to obtain elastomer latex;
wherein the weight ratio of the deionized water to the seed emulsion to the methyl acrylate to the allyl methacrylate to the sodium persulfate to the sodium dodecylbenzenesulfonate is 105;
the number average particle diameter of the elastomer latex is 100nm.
3. Preparation of core-shell graft copolymers: adding elastomer latex, deionized water, butyl methacrylate, sodium persulfate and sodium dodecyl benzene sulfonate into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.085MPa, then filling nitrogen into the closed reaction container until the pressure is 0.14MPa, then starting stirring, controlling the stirring speed to 220rpm, stirring for 1.5h, then continuously filling nitrogen until the pressure is 0.17MPa, and continuously stirring for 1.5h to obtain a graft copolymer emulsion;
wherein the weight ratio of the elastomer latex to the deionized water to the butyl methacrylate to the sodium persulfate to the sodium dodecylbenzenesulfonate is 200;
the number average particle size of the graft copolymer emulsion was 100nm.
4. And (3) post-treatment: adding the graft copolymer emulsion, formaldehyde and a sodium hydroxide aqueous solution with the mass concentration of 30% into a reaction container, heating the temperature to 55 ℃, starting stirring, controlling the stirring speed to 220rpm, stirring for 18min, adding dimethylamine, continuing stirring for 20min, then adding a hydrochloric acid aqueous solution with the mass concentration of 20%, continuing stirring for 12min to obtain a cationized graft copolymer emulsion, performing spray drying on the cationized graft copolymer emulsion, controlling the inlet temperature in the spray drying to be 130 ℃, controlling the outlet temperature to be 70 ℃, and finishing the spray drying to obtain a transparent impact modifier;
wherein the weight ratio of the graft copolymer emulsion to formaldehyde to a 30% sodium hydroxide aqueous solution and dimethylamine to a 20% hydrochloric acid aqueous solution is 410.
Comparative example 1
The preparation method of the transparent impact modifier for polyvinyl chloride described in example 1 was used, except that: in step 1, the addition of the dispersion is omitted in the preparation of the seed emulsion.
Comparative example 2
The preparation method of the transparent impact modifier for polyvinyl chloride described in example 1 was used, except that: and (3) omitting cationization of the graft copolymer emulsion, namely changing the post-treatment of the step (4) into spray drying of the graft copolymer emulsion, controlling the inlet temperature in the spray drying to be 120 ℃ and the outlet temperature to be 60 ℃, and obtaining the transparent impact modifier after the spray drying is finished.
Test examples
The transparent impact modifiers prepared in examples 1-3 and comparative examples 1-2 were mixed with polyvinyl chloride according to the following formulation and parts by weight, respectively:
100 parts of polyvinyl chloride, 5 parts of transparent impact modifier, 3 parts of calcium-zinc stabilizer, 2 parts of tributyl citrate, 1 part of chlorinated polyethylene and 0.5 part of oxidized polypropylene wax;
then placing the mixture in a high-speed mixer for high-speed mixing, controlling the temperature during high-speed mixing to be 120 ℃, the mixing speed to be 500rpm, the mixing time to be 20min, discharging and cooling after the high-speed mixing is finished to prepare a standard test sample, and then testing the notched impact strength, the haze, the light transmittance, the notched impact strength at-15 ℃, the elongation at break, the tensile strength and the bending strength of the standard test sample at 25 ℃, wherein the test results are as follows:
then, standing the standard test sample at 55 ℃ for 100d, and testing the notch impact strength, the haze, the light transmittance, the tensile strength and the bending strength of the standard test sample at 25 ℃, wherein the test results are as follows:
from the above results, it can be seen that the omission of the dispersion in the preparation of the seed emulsion affects the haze, light transmittance and high temperature resistance of polyvinyl chloride, while the omission of the cationization of the graft copolymer emulsion affects the notched impact strength at 25 ℃, notched impact strength at-15 ℃, elongation at break, tensile strength, flexural strength and high temperature resistance of polyvinyl chloride;
the modified pregelatinized starch is mainly used in the dispersion liquid, can promote the preparation of the seed emulsion and can improve the transparency and the high temperature resistance of the prepared seed emulsion; and the cationization of the graft copolymer emulsion can enhance the stability of the transparent impact modifier prepared in the later period and enhance the bonding strength between the transparent impact modifier and the polyvinyl chloride.
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for preparing a transparent impact modifier for polyvinyl chloride is characterized by comprising the following steps: preparing seed emulsion, preparing elastomer, preparing core-shell graft copolymer, and post-treating;
adding deionized water, styrene, propyl methacrylate, sodium persulfate, sodium dodecyl benzene sulfonate and dispersion into a closed reaction container, vacuumizing the closed reaction container until the vacuum degree is 0.07-0.08MPa, then filling nitrogen into the closed reaction container until the pressure is 0.14-0.16MPa, starting stirring, and stirring to obtain seed emulsion;
adding deionized water and pregelatinized starch into a reaction vessel, heating to 50-55 ℃, starting stirring, adding a sodium hydroxide aqueous solution with the mass concentration of 28-30%, stirring, heating to 80-85 ℃, adding potassium persulfate, continuing stirring, adding sodium bisulfite, continuing stirring, adding sodium tripolyphosphate, and continuing stirring to obtain a dispersion liquid;
and the post-treatment comprises the steps of adding the graft copolymer emulsion, formaldehyde and a sodium hydroxide aqueous solution with the mass concentration of 28-30% into a reaction container, heating the temperature to 50-55 ℃, starting stirring, adding dimethylamine, continuing stirring, then adding a hydrochloric acid aqueous solution with the mass concentration of 18-20%, continuing stirring to obtain a cationized graft copolymer emulsion, carrying out spray drying on the cationized graft copolymer emulsion, and obtaining the transparent impact modifier after the spray drying is finished.
2. The method of claim 1, wherein the weight ratio of deionized water, styrene, propyl methacrylate, potassium persulfate, sodium dodecylbenzenesulfonate, and the dispersion in preparing the seed emulsion is 100-105.
3. The method for preparing a transparent impact modifier for polyvinyl chloride according to claim 1, wherein in the preparation of the dispersion, the weight ratio of deionized water, pregelatinized starch, 28-30% by mass of aqueous sodium hydroxide solution, potassium persulfate, sodium bisulfite and sodium tripolyphosphate is 400-420.
4. The method of preparing a transparent impact modifier for polyvinyl chloride according to claim 1, wherein the preparing of the elastomer comprises adding deionized water, seed emulsion, methyl acrylate, allyl methacrylate, sodium persulfate, and sodium dodecylbenzenesulfonate into a closed reaction vessel, vacuumizing the closed reaction vessel to a vacuum degree of 0.08-0.085MPa, then charging nitrogen into the closed reaction vessel to a pressure of 0.13-0.15MPa, then starting stirring and controlling the stirring speed to 200-220rpm, and stirring for 2.5-3h to obtain elastomer latex.
5. The method of claim 4, wherein the weight ratio of the deionized water, the seed emulsion, the methyl acrylate, the allyl methacrylate, the sodium persulfate, and the sodium dodecylbenzenesulfonate in the elastomer preparation is from 100 to 105 to 35 to 1.
6. The method of claim 1, wherein the preparation of the core-shell graft copolymer comprises adding elastomer latex, deionized water, butyl methacrylate, sodium persulfate, and sodium dodecylbenzenesulfonate into a closed reaction vessel, vacuumizing the closed reaction vessel to a vacuum degree of 0.08-0.085MPa, charging nitrogen into the closed reaction vessel to a pressure of 0.12-0.14MPa, controlling the stirring speed to 200-220rpm, stirring for 1-1.5h, continuing to charge nitrogen to a pressure of 0.15-0.17MPa, and continuing to stir for 1-1.5h to obtain a graft copolymer emulsion.
7. The method of claim 6, wherein the weight ratio of the elastomer latex, the deionized water, the butyl methacrylate, the sodium persulfate, and the sodium dodecylbenzenesulfonate in the preparation of the core-shell graft copolymer is 190-200.
8. The method of claim 1, wherein in the post-treatment, the weight ratio of the graft copolymer emulsion, formaldehyde, 28-30% by mass aqueous sodium hydroxide solution, dimethylamine, 18-20% by mass aqueous hydrochloric acid solution is 400-410.
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| CN117534924A (en) * | 2023-11-24 | 2024-02-09 | 浙江奕科新材料股份有限公司 | Light environment-friendly plastic floor and preparation method thereof |
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| CN115340638B (en) | 2023-01-03 |
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