CN116731257A - Acrylic ester-chloroethylene copolymerization paste resin and preparation method thereof - Google Patents
Acrylic ester-chloroethylene copolymerization paste resin and preparation method thereof Download PDFInfo
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- CN116731257A CN116731257A CN202310780950.XA CN202310780950A CN116731257A CN 116731257 A CN116731257 A CN 116731257A CN 202310780950 A CN202310780950 A CN 202310780950A CN 116731257 A CN116731257 A CN 116731257A
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- 239000011347 resin Substances 0.000 title claims abstract description 36
- 229920005989 resin Polymers 0.000 title claims abstract description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 59
- 238000007334 copolymerization reaction Methods 0.000 title claims description 32
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 71
- 239000004816 latex Substances 0.000 claims abstract description 56
- 229920000126 latex Polymers 0.000 claims abstract description 56
- 239000003999 initiator Substances 0.000 claims abstract description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 31
- 229920001577 copolymer Polymers 0.000 claims abstract description 19
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 10
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000013530 defoamer Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 84
- 239000000839 emulsion Substances 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 36
- 230000001276 controlling effect Effects 0.000 claims description 23
- 230000001804 emulsifying effect Effects 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002518 antifoaming agent Substances 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 230000000844 anti-bacterial effect Effects 0.000 claims description 9
- 239000003899 bactericide agent Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- -1 hydroxy vinyl Chemical group 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- LGNQGTFARHLQFB-UHFFFAOYSA-N 1-dodecyl-2-phenoxybenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OC1=CC=CC=C1 LGNQGTFARHLQFB-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 12
- 229920000915 polyvinyl chloride Polymers 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 4
- 239000004709 Chlorinated polyethylene Substances 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001944 Plastisol Polymers 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004999 plastisol Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- 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
Abstract
The invention belongs to the field of paste resins, and particularly relates to an acrylic ester-vinyl chloride copolymer paste resin which comprises the following raw materials in parts by weight: 2500-7500 parts of deionized water, 2500-7500 parts of polyacrylate seed latex, 2500-7500 parts of vinyl chloride monomer, 5-15 parts of initiator, 1-2 parts of EDTA, 350-400 parts of emulsifier I, 3-7 parts of sodium bicarbonate with the mass fraction of 25%, 0.1-0.5 part of ferrous sulfate, 4-8 parts of defoamer and 30-50 parts of sodium hydroxide with the mass fraction of 10%. Compared with the prior art, the invention has the beneficial effects that: the copolymer paste resin obtained by adopting the formula and the process has excellent performance, wherein the viscosity can reach 1604mPa.s, the tensile strength can reach 45.4MPa, the elongation at break can reach 465%, and the glass transition temperature can reach 55 ℃.
Description
Technical Field
The invention belongs to the field of paste resins, and particularly relates to an acrylic ester-vinyl chloride copolymer paste resin and a preparation method thereof.
Background
Polyvinyl chloride paste resins are generally prepared into plastisol for further processing, and the plastisol can be used to obtain polyvinyl chloride plastic products only through a heating process, and are mainly used for producing gloves, artificial leather, coating cloth, floors, conveyor belts, wallpaper, labels, shoes, toys and the like.
The polyvinyl chloride has poor thermal stability and mechanical property, and the pure hard polyvinyl chloride belongs to a hard and brittle material; the plasticizer of the soft polyvinyl chloride has larger mobility and is easy to break in the use process. In order to increase the mechanical property in the polyvinyl chloride processing process, expensive acrylic ester copolymer, chlorinated polyethylene and other auxiliary agents are additionally added, so that the cost of a polyvinyl chloride finished product is increased, and the actual effect is not ideal due to poor compatibility of the acrylic ester copolymer, the chlorinated polyethylene and the polyvinyl chloride.
Disclosure of Invention
In order to solve the problems mentioned in the background art, the invention provides an acrylic ester-chloroethylene copolymerization paste resin, which comprises the following raw materials in parts by weight: 2500-7500 parts of deionized water, 2500-7500 parts of polyacrylate seed latex, 2500-7500 parts of vinyl chloride monomer, 5-15 parts of initiator, 1-2 parts of EDTA, 350-400 parts of emulsifier I, 3-7 parts of sodium bicarbonate with the mass fraction of 25%, 0.1-0.5 part of ferrous sulfate, 4-8 parts of defoamer and 30-50 parts of sodium hydroxide with the mass fraction of 10%.
Preferably, the polyacrylate seed latex comprises the following raw materials in parts by weight: 6000-7000 parts of deionized water, 500-700 parts of emulsifying agent, 3000-5000 parts of butyl acrylate, 200-300 parts of methyl methacrylate, 50-150 parts of acrylic acid, 100-150 parts of hydroxyethyl acrylate, 30-40 parts of initiator, 40-60 parts of 10% sodium hydroxide, 3-7 parts of ammonium bicarbonate, 4-8 parts of defoamer and 4-8 parts of bactericide.
Preferably, the emulsifier comprises an emulsifier I, an emulsifier S and an emulsifier A, wherein the emulsifier I is sodium dodecyl benzene sulfonate, the emulsifier S is sodium dodecyl diphenyl ether sulfonate, and the emulsifier A is sodium 2-hydroxy-3-allyloxypropane sulfonate;
the initiator is any one of potassium persulfate, sodium persulfate and ammonium persulfate;
the defoaming agent is mineral oil defoaming agent;
the bactericide is thiazolinone.
Preferably, the preparation process of the polyacrylate seed latex comprises the following steps:
preparation of a pre-emulsion: adding deionized water into a pre-emulsifying kettle, starting stirring, adding an emulsifier S, an emulsifier A and more than 60% of an emulsifier I into the pre-emulsifying kettle, stirring until the solution is transparent, adding butyl acrylate, methyl methacrylate, acrylic acid and hydroxy vinyl acrylate into the pre-emulsifying kettle, and stirring to emulsify to form a stable pre-emulsion for later use;
preparation of latex initiator solution: adding deionized water, an initiator and ammonium bicarbonate into a latex initiator dropwise adding tank, and stirring until the solution is transparent for later use;
polymerization: spraying an antiscaling agent from the top of an external condenser of a polymerization kettle, adding deionized water into the polymerization kettle, starting stirring, adding the rest of emulsifier I into the polymerization kettle, heating to 75-85 ℃, adding a pre-emulsion with the concentration of less than 10% and a latex initiator solution with the concentration of less than 20%, controlling the polymerization reaction temperature to 80-90 ℃, performing polymerization reaction, forming a white-colored blue-light emulsion in the polymerization kettle, adding dropwise the rest of pre-emulsion and 70-80% of the latex initiator solution into the polymerization kettle, controlling the dropwise adding time to 1-4h, controlling the reaction temperature to 80-90 ℃, adding the rest of the latex initiator solution into the polymerization kettle after the dropwise adding reaction is finished, performing polymerization heat preservation for 0.5-2h, and performing heat preservation on the polymerization kettle to 80-90 ℃;
post-treatment: cooling to below 40 ℃ after the heat preservation of the polymerization kettle is finished, regulating the pH value of the emulsion to 7-8 by using 10% sodium hydroxide solution, adding a defoaming agent and a bactericide into the polymerization kettle, and filtering and discharging by using a 180-mesh screen.
Preferably, the weight ratio of the polyacrylate seed latex to the vinyl chloride monomer is 1:1.
The invention also provides a preparation method of the acrylic ester-vinyl chloride copolymer paste resin, which comprises the following steps:
adding deionized water and initiator sodium persulfate into a copolymerization initiator tank, and stirring until the solution is transparent for later use;
preparation of a copolymerization emulsion: adding deionized water and an emulsifier I into a copolymerization emulsifier tank, and stirring until the solution is transparent for later use;
copolymerization: spraying an antiscaling agent from the top of an external condenser of the copolymerization kettle, adding deionized water and polyacrylate seed latex into the copolymerization kettle, uniformly stirring, adding 10% sodium hydroxide by mass fraction to adjust the pH value to 8-9, adding sodium bicarbonate by mass fraction of sodium bicarbonate, and vacuumizing for deoxidization, wherein the vacuum degree is not lower than-0.08 MPa;
heating to 40-60 ℃, adding vinyl chloride monomer, dropwise adding copolymerization initiator solution, controlling the polymerization temperature to be 50-60 ℃, controlling the polymerization pressure to be 0.5-1MPa, and dropwise adding copolymerization emulsion after polymerization reaction to be 20-40 min;
when the polymerization pressure is reduced, heating to 60-80 ℃, continuing to react for 30-50min, adding a defoaming agent, vacuumizing, cooling to below 40 ℃, discharging and drying.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention relies on the mature polyvinyl chloride paste resin production technology, firstly forms polyacrylic latex through a seed emulsion polymerization mode, then copolymerizes to form emulsion with a core-shell structure by taking polyacrylate as a core and polyvinyl chloride as a shell, the emulsion has weather resistance and intrinsic fire resistance, and finally dries to form polyacrylate-vinyl chloride copolymerization paste resin. The resin has good compatibility with polyvinyl chloride, low price, can be used as a mechanical property improvement auxiliary agent of the polyvinyl chloride, has good toughening effect, and can replace chlorinated polyethylene and acrylic ester copolymer products used in the current market.
2. The copolymer paste resin obtained by adopting the formula and the process has excellent performance, wherein the viscosity can reach 1604mPa.s, the tensile strength can reach 45.4MPa, the elongation at break can reach 465%, and the glass transition temperature can reach 55 ℃.
Detailed Description
The reagents used in the invention are all obtained in the market, and the parts are all parts by weight unless otherwise specified.
In the invention, the emulsifier I is sodium dodecyl benzene sulfonate;
the emulsifier S is sodium dodecyl diphenyl ether sulfonate;
the emulsifier A is sodium 2-hydroxy-3-allyloxypropanesulfonate.
Principle of main reaction
Preparation of polyacrylate seed emulsion
Preparation of acrylate-vinyl chloride copolymer paste resin
Preparation example 1
The preparation process of the polyacrylate seed latex comprises the following steps:
preparation of a pre-emulsion: adding 3900 parts of deionized water into a pre-emulsifying kettle, starting stirring, adding 50 parts of an emulsifier S, 50 parts of an emulsifier A and 375 parts of an emulsifier I into the pre-emulsifying kettle, stirring until the solution is transparent, adding 4000 parts of butyl acrylate, 250 parts of methyl methacrylate, 100 parts of acrylic acid and 125 parts of hydroxy vinyl acrylate into the pre-emulsifying kettle, and stirring to emulsify to form stable pre-emulsion for later use;
preparation of latex initiator solution: adding 1510 parts of deionized water, 35 parts of potassium persulfate and 5 parts of ammonium bicarbonate into a latex initiator dropwise adding tank, and stirring until the solution is transparent for later use;
polymerization: spraying an antiscaling agent from the top of an external condenser of a polymerization kettle, adding 1000 parts of deionized water at 80 ℃ into the polymerization kettle, starting stirring, adding 125 parts of the rest of emulsifier I into the polymerization kettle, heating to 80 ℃, adding 4.5% of pre-emulsion (corresponding to 400 parts) and 13% of latex initiator solution (corresponding to 200 parts), controlling the polymerization temperature to 84-86 ℃, carrying out polymerization for 30 min, forming emulsion of white color blue light in the polymerization kettle, adding dropwise the rest of pre-emulsion and 77% of latex initiator solution (corresponding to 1200 parts) into the polymerization kettle, controlling the dropwise adding time to 2.5-3h, controlling the reaction temperature to 82-84 ℃, adding the rest of latex initiator solution into the polymerization kettle after the dropwise adding reaction, carrying out polymerization heat preservation for 1h, and keeping the polymerization kettle at 86-88 ℃;
post-treatment: cooling to below 40 ℃ after the heat preservation of the polymerization kettle is finished, regulating the pH value of the emulsion to 7-7.5 by using 10% sodium hydroxide solution, adding 6 parts of defoamer and 6 parts of bactericide into the polymerization kettle, and filtering and discharging by using a 180-mesh screen.
According to the preparation process of the polyacrylate seed latex of the example, the particle size of the seed is 77.4nm; pH value: 7.5.
preparation example 2
This example differs from example 1 in that "100 parts of emulsifier S, 50 parts of emulsifier A, 375 parts of emulsifier I" and the remainder are identical to preparation example 1.
According to the preparation process of the polyacrylate seed latex of the example, the particle size of the seed is 81.5nm; pH value: 7.2.
preparation example 3
This example differs from example 1 in that "50 parts of emulsifier S, 100 parts of emulsifier A, 375 parts of emulsifier I" and the remainder are identical to preparation example 1.
According to the preparation process of the polyacrylate seed latex of the example, the particle size of the seed is 79.6nm; pH value: 7.4.
preparation example 4
This example differs from example 1 in that "100 parts of emulsifier S, 100 parts of emulsifier A, 375 parts of emulsifier I" and the remainder are identical to preparation example 1.
According to the preparation process of the polyacrylate seed latex of the example, the particle size of the seed is 74.4nm; the method comprises the steps of carrying out a first treatment on the surface of the pH value: 7.3.
preparation example 5
This example differs from example 1 in that "50 parts of emulsifier S, 50 parts of emulsifier A, 275 parts of emulsifier I" and the remainder are identical to preparation example 1.
According to the preparation process of the polyacrylate seed latex of the example, the particle size of the seed is 76.3nm; pH value: 7.2.
preparation example 6
This example differs from example 1 in that "50 parts of emulsifier S, 50 parts of emulsifier A, 475 parts of emulsifier I" and the remainder are identical to preparation example 1.
According to the preparation process of the polyacrylate seed latex of the example, the particle size of the seed is 79.9nm; pH value: 7.3.
preparation example 7
This example is different from example 1 in that "50 parts of emulsifier S, 50 parts of emulsifier A, 425 parts of emulsifier I" ", and the rest is the same as in preparation example 1.
According to the preparation process of the polyacrylate seed latex of the example, the particle size of the seed is 73.4nm; pH value: 7.1.
preparation example 8
The preparation process of the polyacrylate seed latex comprises the following steps:
preparation of a pre-emulsion: adding 3500 parts of deionized water into a pre-emulsifying kettle, starting stirring, adding 50 parts of an emulsifier S, 50 parts of an emulsifier A and 300 parts of an emulsifier I into the pre-emulsifying kettle, stirring until the solution is transparent, adding 3000 parts of butyl acrylate, 200 parts of methyl methacrylate, 50 parts of acrylic acid and 100 parts of hydroxy vinyl acrylate into the pre-emulsifying kettle, and stirring to emulsify to form stable pre-emulsion for later use;
preparation of latex initiator solution: adding 1500 parts of deionized water, 30 parts of potassium persulfate and 3 parts of ammonium bicarbonate into a latex initiator dropwise adding tank, and stirring until the solution is transparent for later use;
polymerization: spraying an antiscaling agent from the top of an external condenser of a polymerization kettle, then adding 1000 parts of deionized water at 80 ℃ into the polymerization kettle, starting stirring, adding 100 parts of the rest of emulsifier I into the polymerization kettle, heating to 80 ℃, adding 10% of pre-emulsion and 20% of latex initiator solution, controlling the polymerization reaction temperature to 84-86 ℃, carrying out polymerization reaction to 30 min, forming white blue emulsion in the polymerization kettle, adding the rest of pre-emulsion and 70% of latex initiator solution into the polymerization kettle dropwise, controlling the dropwise adding time to 2.5-3h, controlling the reaction temperature to 82-84 ℃, adding the rest of latex initiator solution into the polymerization kettle after the dropwise adding reaction is finished, carrying out polymerization heat preservation for 1h, and keeping the polymerization kettle at the heat preservation temperature to 86-88 ℃;
post-treatment: cooling to below 40 ℃ after the heat preservation of the polymerization kettle is finished, regulating the pH value of the emulsion to 7-7.5 by using 10% sodium hydroxide solution, adding 4 parts of defoamer and 4 parts of bactericide into the polymerization kettle, and filtering and discharging by using a 180-mesh screen.
According to the preparation process of the polyacrylate seed latex of the example, the particle size of the seed is 72.1nm; pH value: 7.5.
preparation example 9
The preparation process of the polyacrylate seed latex comprises the following steps:
preparation of a pre-emulsion: adding 4500 parts of deionized water into a pre-emulsifying kettle, starting stirring, adding 50 parts of an emulsifier S, 50 parts of an emulsifier A and 400 parts of an emulsifier I into the pre-emulsifying kettle, stirring until the solution is transparent, adding 5000 parts of butyl acrylate, 300 parts of methyl methacrylate, 150 parts of acrylic acid and 150 parts of hydroxy vinyl acrylate into the pre-emulsifying kettle, and stirring to emulsify to form stable pre-emulsion for later use;
preparation of latex initiator solution: adding 1500 parts of deionized water, 40 parts of potassium persulfate and 7 parts of ammonium bicarbonate into a latex initiator dropwise adding tank, and stirring until the solution is transparent for later use;
polymerization: spraying an antiscaling agent from the top of an external condenser of a polymerization kettle, then adding 1000 parts of deionized water at 80 ℃ into the polymerization kettle, starting stirring, adding 200 parts of the rest of emulsifier I into the polymerization kettle, heating to 80 ℃, adding 10% of pre-emulsion and 20% of latex initiator solution, controlling the polymerization reaction temperature to 84-86 ℃, carrying out polymerization reaction to 30mi < n >, forming white-colored blue-light emulsion in the polymerization kettle, adding the rest of pre-emulsion and 70% of latex initiator solution into the polymerization kettle dropwise, controlling the dropwise adding time to 2.5-3h, controlling the reaction temperature to 82-84 ℃, adding the rest of latex initiator solution into the polymerization kettle after the dropwise adding reaction is finished, carrying out polymerization heat preservation for 1h, and keeping the polymerization kettle at the heat preservation temperature to 86-88 ℃;
post-treatment: cooling to below 40 ℃ after the heat preservation of the polymerization kettle is finished, regulating the pH value of the emulsion to 7-7.5 by using 10% sodium hydroxide solution, adding 8 parts of defoamer and 8 parts of bactericide into the polymerization kettle, and filtering and discharging by using a 180-mesh screen.
According to the preparation process of the polyacrylate seed latex of the example, the particle size of the seed is 85.3nm; pH value: 7.2.
example 1
The preparation process of the copolymerization paste resin comprises the following steps:
the preparation of a copolymerization initiator solution, which is to add 1000 parts of deionized water and 10 parts of potassium persulfate into a copolymerization initiator tank, and stir the mixture until the solution is transparent for standby;
preparation of a copolymerization emulsion: 1000 parts of deionized water and 375 parts of emulsifier I are added into a copolymerization emulsifier tank, and the mixture is stirred until the solution is transparent for standby;
copolymerization: spraying an antiscaling agent from the top of an external condenser of a copolymerization kettle, adding 5000 parts of deionized water and 5000 parts of polyacrylate seed latex obtained in preparation example 1 into the copolymerization kettle, uniformly stirring, adding 10% sodium hydroxide to adjust the pH value to 8-9, adding 5 parts of white suspended block, 0.3 part of ferrous sulfate, 1.5 parts of EDTA and 200 parts of 25% ammonium bicarbonate by mass, vacuumizing and deoxidizing, wherein the vacuum degree is not lower than-0.08 MPa;
heating to 50 ℃, adding 5000 parts of vinyl chloride monomer, dropwise adding a copolymerization initiator solution, controlling the polymerization temperature to 54 ℃, controlling the polymerization pressure to 0.78MPa, and dropwise adding a copolymerization emulsion after polymerization for 30 min;
and (3) when the polymerization pressure is reduced, heating to 70 ℃, continuing to react for 40min, adding a defoaming agent, vacuumizing, cooling to below 40 ℃, discharging and drying.
Example 2
This example is different from example 1 in that "5000 parts of the polyacrylate seed latex obtained in preparation example 2" and the rest are exactly the same as in example 1.
Example 3
This example is different from example 1 in that "5000 parts of the polyacrylate seed latex obtained in preparation example 3" and the rest are exactly the same as in example 1.
Example 4
This example is different from example 1 in that "5000 parts of the polyacrylate seed latex obtained in preparation example 4" and the rest are exactly the same as in example 1.
Example 5
This example is different from example 1 in that "5000 parts of the polyacrylate seed latex obtained in preparation example 5" and the rest are exactly the same as in example 1.
Example 6
This example is different from example 1 in that "5000 parts of the polyacrylate seed latex obtained in preparation example 6" and the rest are exactly the same as in example 1.
Example 7
This example is different from example 1 in that "5000 parts of the polyacrylate seed latex obtained in preparation example 7" and the rest are exactly the same as in example 1.
Comparative example 1
The preparation process of the paste resin comprises the following steps:
the preparation of an initiator solution, which is to add 1000 parts of deionized water and 10 parts of potassium persulfate into an initiator tank, and stir the mixture until the solution is transparent for standby;
preparation of emulsion: adding 1000 parts of deionized water and 375 parts of emulsifier I into an emulsifier tank, and stirring until the solution is transparent for later use;
polymerization: spraying an antiscaling agent from the top of an external condenser of a polymerization kettle, adding 9732 parts of deionized water, 28.4 parts of an emulsifier S, 28.4 parts of an emulsifier A and 210.4 parts of an emulsifier I into the polymerization kettle, uniformly stirring, adding 10% sodium hydroxide to adjust the pH value to 8-9, adding 5 parts of white suspended solid, 0.3 part of ferrous sulfate, 1.5 parts of EDTA and 200 parts of 25% ammonium bicarbonate by mass, and then vacuumizing for deoxidization, wherein the vacuum degree is not lower than-0.08 MPa;
heating to 50 ℃, adding 5000 parts of vinyl chloride monomer, dropwise adding initiator solution, controlling the polymerization temperature to 54 ℃, controlling the polymerization pressure to 0.78MPa, and dropwise adding emulsion after polymerization for 30 min;
and (3) when the polymerization pressure is reduced, heating to 70 ℃, continuing to react for 40min, adding a defoaming agent, vacuumizing, cooling to below 40 ℃, discharging and drying.
Results and detection
1. Viscosity test of copolypaste resin
The testing method comprises the following steps: 10g of the copolymerized paste resin prepared in examples 1 to 7 and the paste resin of comparative example 1 were each taken, and 6g of a plasticizer (dioctylphthalate) was added correspondingly to prepare pastes, and the viscosity was measured at room temperature (25 ℃) by a rotational viscometer, and the results are shown in Table 1.
TABLE 1
| Project | Viscosity (mPas) |
| Example 1 | 1604 |
| Example 2 | 2134 |
| Example 3 | 1941 |
| Example 4 | 2073 |
| Example 5 | 2256 |
| Example 6 | 2341 |
| Example 7 | 2152 |
| Comparative example 1 | 2865 |
As is clear from Table 1, the viscosity of the copolymer paste resin prepared in the examples of the present invention was 2500 or less at room temperature (25 ℃ C.), and the lowest viscosity was example 1, which was 1604.
2. Mechanical property test of copolymer paste resin
The testing method comprises the following steps: 10g of the copolymerization paste resin prepared in examples 1 to 7 and the paste resin of comparative example 1 were each taken, 6g of plasticizer (dioctylphthalate) was added correspondingly to prepare pastes, and the pastes were plasticized at 180℃for 5 minutes to obtain samples having a thickness of 0.25mm, and the tensile strength and elongation at break were measured at room temperature (25 ℃) by a tensile tester at a tensile rate of 50mm/min, and the results are shown in Table 2.
TABLE 2
| Project | Tensile Strength (MPa) | Elongation at break% |
| Example 1 | 45.4 | 465 |
| Example 2 | 37.1 | 398 |
| Example 3 | 38.2 | 374 |
| Example 4 | 36.8 | 399 |
| Example 5 | 37.5 | 385 |
| Example 6 | 34.1 | 401 |
| Example 7 | 36.8 | 367 |
| Comparative example 1 | 24.2 | 265 |
As is clear from Table 2, the copolymer paste resin prepared in the examples of the present invention has a tensile strength of 30 or more at room temperature (25 ℃ C.), wherein the highest tensile strength is example 1 and the tensile strength thereof is 45.4; the elongation at break of the copolymer paste resin was 350 or more at room temperature (25 ℃ C.), the highest elongation at break being example 10, and the elongation at break was 465.
3. Thermal stability test
The testing method comprises the following steps: 10g of the copolymerization paste resin prepared in examples 1 to 7 and the paste resin of comparative example 1 were each taken, 6g of plasticizer (dioctylphthalate) was added correspondingly to prepare pastes, and the pastes were plasticized at 180℃for 5 minutes to obtain samples having a thickness of 0.25mm, and glass transition temperatures were measured by a thermogravimetric analyzer, and the results are shown in Table 3.
TABLE 3 Table 3
As is clear from Table 3, the glass transition temperatures of the copolymerized paste resins prepared in the examples of the present invention are all 45-65, and the toughness of the products is improved compared with 81 in comparative example 1.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. The acrylic ester-chloroethylene copolymerized paste resin is characterized by comprising the following raw materials in parts by weight: 2500-7500 parts of deionized water, 2500-7500 parts of polyacrylate seed latex, 2500-7500 parts of vinyl chloride monomer, 5-15 parts of initiator, 1-2 parts of EDTA, 350-400 parts of emulsifier I, 3-7 parts of sodium bicarbonate with the mass fraction of 25%, 0.1-0.5 part of ferrous sulfate, 4-8 parts of defoamer and 30-50 parts of sodium hydroxide with the mass fraction of 10%.
2. The acrylic acid ester-vinyl chloride copolymer paste resin as claimed in claim 1, wherein the polyacrylate seed latex comprises the following raw materials in parts by weight: 6000-7000 parts of deionized water, 500-700 parts of emulsifying agent, 3000-5000 parts of butyl acrylate, 200-300 parts of methyl methacrylate, 50-150 parts of acrylic acid, 100-150 parts of hydroxyethyl acrylate, 30-40 parts of initiator, 40-60 parts of 10% sodium hydroxide, 3-7 parts of ammonium bicarbonate, 4-8 parts of defoamer and 4-8 parts of bactericide.
3. An acrylic acid ester-vinyl chloride copolymer paste resin according to claim 1 or 2, wherein said emulsifier comprises an emulsifier i, an emulsifier S and an emulsifier a, said emulsifier i being sodium dodecylbenzenesulfonate, said emulsifier S being sodium dodecyldiphenylether sulfonate, said emulsifier a being sodium 2-hydroxy-3-allyloxypropanesulfonate;
the initiator is any one of potassium persulfate, sodium persulfate and ammonium persulfate;
the defoaming agent is mineral oil defoaming agent;
the bactericide is thiazolinone.
4. The acrylic acid ester-vinyl chloride copolymer paste resin as defined in claim 3, wherein said polyacrylate seed latex is prepared by the following steps:
preparation of a pre-emulsion: adding deionized water into a pre-emulsifying kettle, starting stirring, adding an emulsifier S, an emulsifier A and more than 60% of an emulsifier I into the pre-emulsifying kettle, stirring until the solution is transparent, adding butyl acrylate, methyl methacrylate, acrylic acid and hydroxy vinyl acrylate into the pre-emulsifying kettle, and stirring to emulsify to form a stable pre-emulsion for later use;
preparation of latex initiator solution: adding deionized water, an initiator and ammonium bicarbonate into a latex initiator dropwise adding tank, and stirring until the solution is transparent for later use;
polymerization: spraying an antiscaling agent from the top of an external condenser of a polymerization kettle, adding deionized water into the polymerization kettle, starting stirring, adding the rest of emulsifier I into the polymerization kettle, heating to 75-85 ℃, adding a pre-emulsion with the concentration of less than 10% and a latex initiator solution with the concentration of less than 20%, controlling the polymerization reaction temperature to 80-90 ℃, performing polymerization reaction, forming a white-colored blue-light emulsion in the polymerization kettle, adding dropwise the rest of pre-emulsion and 70-80% of the latex initiator solution into the polymerization kettle, controlling the dropwise adding time to 1-4h, controlling the reaction temperature to 80-90 ℃, adding the rest of the latex initiator solution into the polymerization kettle after the dropwise adding reaction is finished, performing polymerization heat preservation for 0.5-2h, and performing heat preservation on the polymerization kettle to 80-90 ℃;
post-treatment: cooling to below 40 ℃ after the heat preservation of the polymerization kettle is finished, regulating the pH value of the emulsion to 7-8 by using 10% sodium hydroxide solution, adding a defoaming agent and a bactericide into the polymerization kettle, and filtering and discharging by using a 180-mesh screen.
5. The acrylic acid ester-vinyl chloride copolymer paste resin as defined in claim 1, wherein the weight ratio of said acrylic acid ester seed latex to vinyl chloride monomer is 1:1.
6. The method for producing an acrylic acid ester-vinyl chloride copolymer paste resin according to any one of claims 1 to 5, wherein the process for producing the copolymer paste resin comprises:
adding deionized water and initiator sodium persulfate into a copolymerization initiator tank, and stirring until the solution is transparent for later use;
preparation of a copolymerization emulsion: adding deionized water and an emulsifier I into a copolymerization emulsifier tank, and stirring until the solution is transparent for later use;
copolymerization: spraying an antiscaling agent from the top of an external condenser of the copolymerization kettle, adding deionized water and polyacrylate seed latex into the copolymerization kettle, uniformly stirring, adding 10% sodium hydroxide by mass fraction to adjust the pH value to 8-9, adding sodium bicarbonate by mass fraction of sodium bicarbonate, and vacuumizing for deoxidization, wherein the vacuum degree is not lower than-0.08 MPa;
heating to 40-60 ℃, adding vinyl chloride monomer, dropwise adding copolymerization initiator solution, controlling the polymerization temperature to be 50-60 ℃, controlling the polymerization pressure to be 0.5-1MPa, and dropwise adding copolymerization emulsion after 20-40min of polymerization reaction;
when the polymerization pressure is reduced, heating to 60-80 ℃, continuing to react for 30-50min, adding a defoaming agent, vacuumizing, cooling to below 40 ℃, discharging and drying.
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