CN113956410A - Bio-based polyvinyl acetate emulsion and preparation method thereof - Google Patents
Bio-based polyvinyl acetate emulsion and preparation method thereof Download PDFInfo
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- 239000000839 emulsion Substances 0.000 title claims abstract description 54
- 229920002689 polyvinyl acetate Polymers 0.000 title claims abstract description 36
- 239000011118 polyvinyl acetate Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000004945 emulsification Methods 0.000 title description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 20
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960002703 undecylenic acid Drugs 0.000 claims abstract description 18
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920002261 Corn starch Polymers 0.000 claims abstract description 14
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 14
- 239000008120 corn starch Substances 0.000 claims abstract description 14
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 13
- 239000003899 bactericide agent Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 241000276489 Merlangius merlangus Species 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 2
- DDNCQMVWWZOMLN-IRLDBZIGSA-N Vinpocetine Chemical compound C1=CC=C2C(CCN3CCC4)=C5[C@@H]3[C@]4(CC)C=C(C(=O)OCC)N5C2=C1 DDNCQMVWWZOMLN-IRLDBZIGSA-N 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 1
- 229960000744 vinpocetine Drugs 0.000 claims 1
- 239000002023 wood Substances 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000003208 petroleum Substances 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000004014 plasticizer Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 241000863480 Vinca Species 0.000 description 1
- 229920001587 Wood-plastic composite Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- -1 dodecanol ester Chemical class 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000011155 wood-plastic composite Substances 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a bio-based polyvinyl acetate emulsion and a preparation method thereof, and the method achieves the synthesis of the emulsion by introducing bio-based raw materials of corn starch and the copolymerization of undecylenic acid and vinyl acetate. The bio-based polyvinyl acetate emulsion comprises the following components in parts by weight: 10-20 parts of vinyl acetate, 3-5 parts of polyvinyl alcohol, 5-20 parts of undecylenic acid, 5-10 parts of corn starch, 5-10 parts of 1200-mesh coarse whiting, 0.2-0.5 part of initiator, 40-50 parts of deionized water, 0.1 part of bactericide and 0.1 part of defoaming agent. The bio-based polyvinyl acetate emulsion prepared by the formula and the process has the advantages that the lowest film forming temperature is below 0 ℃, no petroleum plasticizer is required to be added, the client-side use environment is wide, the national ten-ring environmental protection standard is met, and the dry and wet strength of the bio-based polyvinyl acetate emulsion passes the HGT2727-2010 polyvinyl acetate emulsion wood adhesive standard test.
Description
Technical Field
The invention belongs to the technical field of emulsion polymerization, and particularly relates to a bio-based polyvinyl acetate emulsion and a preparation method thereof.
Background
Bio-based chemicals and bio-based materials are one of the new material hotspots in the world today and are one of the important methods for solving the environmental and resource problems, and from the technical point of view, almost all industrial materials made of fossil resources can be replaced by bio-based materials instead of petroleum-based materials.
The bio-based material refers to a high molecular material formed by obtaining a biopolymer material or a monomer through biotransformation with a renewable raw material and then further polymerizing. The bio-based material comprises a bio-based platform compound, bioplastic, functional saccharide, a wood-plastic composite material and the like, and has the characteristics of renewable resources, environmental friendliness, carbon reduction and biodegradability which are not possessed by the traditional high polymer material.
The traditional polyvinyl acetate emulsion, namely white latex, has the advantages of simple production process, low price, high bonding strength and the like, is widely used in the fields of wood processing, wood products (decorative wood, woodwork, artificial boards and the like), furniture assembly, packaging and decorative material manufacturing, paper product processing, fabric bonding, label fixing, tobacco processing, tile sticking and the like, and is one of the bulk products in the adhesive industry. The main synthetic raw materials of the polyvinyl acetate emulsion adhesive comprise monomers, a dispersion medium, an initiator, an emulsifier, a protective colloid, a plasticizer, a regulator, a filler, a defoaming agent, a freeze-thaw stabilizer and the like. All that is used is essentially petroleum-based raw materials.
The vegetable oil is used as a renewable green raw material, and potential reactive groups in the chemical structure of the vegetable oil can be used for modification to obtain a bio-based reaction raw material. Castor oil is vegetable oil extracted from castor seeds, undecylenic acid can be obtained by pyrolysis of castor oil, has an allyl structure in the structure, and can be subjected to polymerization reaction with a vinyl acetate monomer to replace a petroleum-based monomer. The development of the bio-based polyvinyl acetate emulsion can well accord with the sustainable development concept.
Disclosure of Invention
The invention aims to provide a bio-based polyvinyl acetate emulsion and a preparation method thereof, aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme: a bio-based polyvinyl acetate emulsion comprising, in parts by weight: 10-20 parts of vinyl acetate, 3-5 parts of polyvinyl alcohol, 5-20 parts of undecylenic acid, 5-10 parts of corn starch, 5-10 parts of 1200-mesh coarse whiting, 0.2-0.5 part of initiator, 40-50 parts of deionized water, 0.1 part of bactericide and 0.1 part of defoaming agent.
Further, the polyvinyl alcohol is formed by mixing one or two of vinca BP-24 and BP-17 according to any proportion.
Further, the initiator is 20 wt% to 50 wt% of ammonium persulfate aqueous solution.
Further, the method specifically comprises the following steps:
(1) material taking: 10-20 parts of vinyl acetate, 3-5 parts of polyvinyl alcohol, 5-20 parts of undecylenic acid, 5-10 parts of corn starch, 5-10 parts of 1200-mesh coarse whiting, 0.2-0.5 part of initiator, 40-50 parts of deionized water, 0.1 part of bactericide and 0.1 part of defoaming agent.
(2) Dissolving polyvinyl alcohol: adding 40-50 parts of deionized water into a reaction kettle, adding 3-5 parts of polyvinyl alcohol and 5-10 parts of corn starch, uniformly stirring, heating to 85-95 ℃, preserving heat for more than 1 hour, and cooling to 75-80 ℃.
(3) Emulsion polymerization: uniformly mixing 10-20 parts of vinyl acetate and 5-20 parts of undecylenic acid to obtain a mixed monomer, and simultaneously dropwise adding the mixed monomer and an initiator into a reaction kettle for 3-4 hours at the dropping temperature of 78-82 ℃; and after the dropwise adding is finished, heating to 85-90 ℃ to obtain the emulsion.
(4) Post-addition: and (3) cooling the emulsion obtained in the step (3) to 50 ℃, adding 5-10 parts of 1200-mesh coarse whiting, 0.1 part of defoaming agent and 0.1 part of bactericide, and filtering to obtain the bio-based polyvinyl acetate emulsion.
The invention has the beneficial effects that:
(1) the invention adopts the copolymerization of a bio-based raw material, namely undecylenic acid and vinyl acetate. The structural characteristics of the bio-based raw material undecylenic acid introduced into the formula are that long-chain unsaturated fatty acid is contained, compared with acrylic acid, maleic anhydride and other monomers which are frequently used in common polyvinyl acetate emulsion, the acidity is low, on one hand, the corrosion to equipment and the damage to a human body are reduced, on the other hand, the long chain segment of the undecylenic acid is copolymerized with vinyl acetate, so that a high polymer is introduced into a flexible chain segment, the flexibility of the molecular chain segment is improved, the vitrification temperature of the polymer emulsion is effectively reduced, and a petroleum-based plasticizer or a polymerization monomer is not required to be added into a finished product, and the soft monomers of butyl acrylate and dibutyl maleate are added. The long chain segment has great moving capacity, and the polymer has unique chemical performance, high flexibility, high hydrophobicity and high heat resistance.
(2) The bio-based polyvinyl acetate emulsion prepared by the formula composition and the process has the lowest film forming temperature below 0 ℃, does not need to add petroleum plasticizer, has wide client use environment, meets the national ten-ring environmental protection standard, and has the dry and wet strength passing the HGT 2727-one-function polyvinyl acetate emulsion wood adhesive standard test.
Detailed Description
The invention introduces a bio-based material, and provides a bio-based polyvinyl acetate emulsion and a preparation method thereof. In order to make the purpose and technical solutions of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly described below.
Example 1
(1) Material taking: 150g of vinyl acetate, 30g of polyvinyl alcohol, 100g of undecylenic acid, 60g of corn starch, 60g of 1200-mesh coarse whiting, 2g of ammonium persulfate, 400g of deionized water, 1g of bactericide and 1g of defoaming agent.
(2) Dissolving polyvinyl alcohol: adding 400g of deionized water into a reaction kettle, adding 30g of polyvinyl alcohol and 60g of corn starch, uniformly stirring, heating to 85-95 ℃, preserving heat for more than 1h, and cooling to 75-80 ℃.
(3) Emulsion polymerization: uniformly mixing 150g of vinyl acetate and 100g of undecylenic acid to obtain a mixed monomer, and simultaneously dropwise adding the mixed monomer and an initiator into a reaction kettle for 3-4 h, wherein the dropwise adding temperature is controlled to be 78-82 ℃; and after the dropwise adding is finished, heating to 85-90 ℃ to obtain the emulsion.
(4) Post-addition: and (3) cooling the emulsion obtained in the step (3) to 50 ℃, adding 60g of 1200-mesh coarse whiting, 1g of defoaming agent and 1g of bactericide, and filtering to obtain the bio-based polyvinyl acetate emulsion.
According to the physical property index of the bio-based polyvinyl acetate emulsion prepared in example 1, the lowest film forming temperature is tested according to the test method standard of GB/T11175-2002 synthetic resin emulsion, and the dry and wet strength results of the standard test of HGT2727-2010 polyvinyl acetate emulsion wood adhesive are shown in Table 1.
Example 2
(1) Material taking: 200g of vinyl acetate, 40g of polyvinyl alcohol, 70g of undecylenic acid, 80g of corn starch, 50g of 1200-mesh coarse whiting, 3g of ammonium persulfate, 450g of deionized water, 1g of bactericide and 1g of defoaming agent.
(2) Dissolving polyvinyl alcohol: adding 450g of deionized water into a reaction kettle, adding 40g of polyvinyl alcohol and 80g of corn starch, uniformly stirring, heating to 85-95 ℃, preserving heat for more than 1 hour, and cooling to 75-80 ℃.
(3) Emulsion polymerization: uniformly mixing 200g of vinyl acetate and 70g of undecylenic acid to obtain a mixed monomer, and simultaneously dropwise adding the mixed monomer and an initiator into a reaction kettle for 3-4 h, wherein the dropwise adding temperature is controlled to be 78-82 ℃; and after the dropwise adding is finished, heating to 85-90 ℃ to obtain the emulsion.
(4) Post-addition: and (3) cooling the emulsion obtained in the step (3) to 50 ℃, adding 50g of 1200-mesh coarse whiting, 1g of defoaming agent and 1g of bactericide, and filtering to obtain the bio-based polyvinyl acetate emulsion.
According to the physical property index of the bio-based polyvinyl acetate emulsion prepared in the example 2, the lowest film forming temperature is tested according to the test method standard of GB/T11175-2002 synthetic resin emulsion, and the dry and wet strength results of the standard test of HGT2727-2010 polyvinyl acetate emulsion wood adhesive are shown in Table 1.
Example 3
(1) Material taking: 100g of vinyl acetate, 40g of polyvinyl alcohol, 150g of undecylenic acid, 50g of corn starch, 80g of 1200-mesh heavy calcium, 4g of ammonium persulfate, 460g of deionized water, 1g of bactericide and 1g of defoaming agent.
(2) Dissolving polyvinyl alcohol: adding 460g of deionized water into a reaction kettle, adding 40g of polyvinyl alcohol and 50g of corn starch, uniformly stirring, heating to 85-95 ℃, preserving heat for more than 1 hour, and cooling to 75-80 ℃.
(3) Emulsion polymerization: uniformly mixing 100g of vinyl acetate and 150g of undecylenic acid to obtain a mixed monomer, and simultaneously dropwise adding the mixed monomer and an initiator into a reaction kettle for 3-4 h, wherein the dropwise adding temperature is controlled to be 78-82 ℃; and after the dropwise adding is finished, heating to 85-90 ℃ to obtain the emulsion.
(4) Post-addition: and (3) cooling the emulsion obtained in the step (3) to 50 ℃, adding 80g of 1200-mesh coarse whiting, 1g of defoaming agent and 1g of bactericide, and filtering to obtain the bio-based polyvinyl acetate emulsion.
According to the physical property index of the bio-based polyvinyl acetate emulsion prepared in the example 3, the lowest film forming temperature is tested according to the test method standard of GB/T11175-2002 synthetic resin emulsion, and the dry and wet strength results of the standard test of HGT2727-2010 polyvinyl acetate emulsion wood adhesive are shown in Table 1.
Table 1: bio-based polyvinyl acetate emulsion performance test
| Index (I) | Example 1 | Example 2 | Example 3 |
| Appearance of the product | Pure white emulsion | Pure white emulsion | Pure white emulsion |
| pH value | 7.02 | 6.98 | 7.1 |
| Viscosity of the oil | 2.5pa.s | 3pa.s | 2.8pa.s |
| Voc | 50ppm | 80ppm | 60ppm |
| Minimum film formation temperature | 0℃ | 2℃ | -2℃ |
| Free formaldehyde | Not detected out | Not detected out | Not detected out |
| Dry strength | 11.9 | 13.2 | 12.5 |
| Wet strength | 5.2 | 6.0 | 5.8 |
As can be seen from the test data in Table 1, the bio-based polyvinyl acetate emulsion prepared by the invention meets the use requirements of the polyvinyl acetate emulsion as the adhesive for wood, and meets the dry and wet strength in the application requirements. And the environmental protection requirement meets the ten-ring standard. Different from the common polyvinyl acetate emulsion, the lowest film forming temperature can be lower than 5 ℃ mostly without adding any petroleum-based o-benzene plasticizer or dodecanol ester film forming auxiliary agent, and the client side has wide application environment range.
It is to be understood that the described embodiments of the invention are intended to be illustrative of some, but not all, embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (4)
1. The bio-based polyvinyl acetate emulsion is characterized by comprising the following components in parts by weight: 10-20 parts of vinyl acetate, 3-5 parts of polyvinyl alcohol, 5-20 parts of undecylenic acid, 5-10 parts of corn starch, 5-10 parts of 1200-mesh coarse whiting, 0.2-0.5 part of initiator, 40-50 parts of deionized water, 0.1 part of bactericide, 0.1 part of defoaming agent and the like.
2. The bio-based polyvinyl acetate emulsion according to claim 1, wherein the polyvinyl alcohol is composed of one or two of vinpocetine BP-24 and BP-17 mixed in any proportion.
3. The bio-based polyvinyl acetate emulsion according to claim 1, wherein the initiator is 20 wt% to 50 wt% aqueous solution of persulfate.
4. The preparation method of the bio-based polyvinyl acetate emulsion according to claim 1, which comprises the following steps:
(1) material taking: 10-20 parts of vinyl acetate, 3-5 parts of polyvinyl alcohol, 5-20 parts of undecylenic acid, 5-10 parts of corn starch, 5-10 parts of 1200-mesh coarse whiting, 0.2-0.5 part of initiator, 40-50 parts of deionized water, 0.1 part of bactericide and 0.1 part of defoaming agent.
(2) Dissolving polyvinyl alcohol: adding 40-50 parts of deionized water into a reaction kettle, adding 3-5 parts of polyvinyl alcohol and 5-10 parts of corn starch, uniformly stirring, heating to 85-95 ℃, preserving heat for more than 1 hour, and cooling to 75-80 ℃.
(3) Emulsion polymerization: uniformly mixing 10-20 parts of vinyl acetate and 5-20 parts of undecylenic acid to obtain a mixed monomer, and simultaneously dropwise adding the mixed monomer and an initiator into a reaction kettle for 3-4 hours at the dropping temperature of 78-82 ℃; and after the dropwise adding is finished, heating to 85-90 ℃ to obtain the emulsion.
(4) Post-addition: and (3) cooling the emulsion obtained in the step (3) to 50 ℃, adding 5-10 parts of 1200-mesh coarse whiting, 0.1 part of defoaming agent and 0.1 part of bactericide, and filtering to obtain the bio-based polyvinyl acetate emulsion.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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