CN113461853A - Environment-friendly plate alignment adhesive polymerization emulsion and preparation method thereof - Google Patents
Environment-friendly plate alignment adhesive polymerization emulsion and preparation method thereof Download PDFInfo
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- CN113461853A CN113461853A CN202110709685.7A CN202110709685A CN113461853A CN 113461853 A CN113461853 A CN 113461853A CN 202110709685 A CN202110709685 A CN 202110709685A CN 113461853 A CN113461853 A CN 113461853A
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- 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
- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
- C09J131/00—Adhesives based on 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an environment-friendly plate alignment adhesive polymerization emulsion and a preparation method thereof. The emulsion for the plate alignment adhesive is characterized in that carboxyl modified polyvinyl alcohol is used as a protective colloid, epichlorohydrin is used as a special cross-linking agent, and the emulsion has the characteristics of no aldehyde, environmental protection and capability of being tested by a JAS111 method for stripping rate.
Description
Technical Field
The invention belongs to the technical field of wood gluing, and particularly relates to an environment-friendly plate splicing glue polymerization emulsion and a preparation method thereof.
Background
The wood-splicing glue is an adhesive used for splicing solid wood products, and is suitable for splicing and tooth-jointing solid wood furniture, solid wood plates, laminated wood, wood artware and wood products, assembling and bonding tables, chairs, doors, windows and stairs and the like. The plate alignment adhesive is usually two-component and consists of a main agent and a curing agent, wherein the main agent is milky polymer emulsion, and the curing agent is generally light brown isocyanate.
The core part of the jigsaw is the polymerization emulsion of the main rubber. In order to improve the water-resistant and heat-resistant performance of the polymerized emulsion, functional monomers are added in the polymerization. The functional monomer is generally an acrylic monomer containing a reactive group such as a hydroxyl group, a carboxyl group, an epoxy group, an amino group, etc. Among them, N-methylolacrylamide is an important functional monomer, and its molecule has a double bond conjugated with a carbonyl group and a highly reactive methylol group, and is a crosslinkable monomer having a wide range of applications. N-methylolacrylamide is necessary to obtain a water-and heat-resistant polymeric emulsion. However, N-methylol acrylamide is prepared by condensation reaction of acrylamide and 37% formaldehyde under weak alkaline condition, the formaldehyde content is high, even if the N-methylol acrylamide participates in polymerization reaction, the free formaldehyde content of the obtained polymerization emulsion can not reach the decacyclo standard (less than or equal to 0.05g/kg), and the environmental protection performance is poor.
Disclosure of Invention
The invention aims to provide an environment-friendly plate alignment adhesive polymerization emulsion and a preparation method thereof, aiming at the defect that in the prior art, most of polymerization emulsions using N-hydroxymethyl acrylamide as a crosslinking monomer have the environmental protection problem that the free formaldehyde content does not reach the decacyclic standard. The invention improves the water-resistant and heat-resistant performance (passing the stripping rate test) of the polymerized emulsion and ensures that the content of free formaldehyde reaches the environmental protection of the ten-ring standard.
The purpose of the invention is realized by the following technical scheme: an environment-friendly plate alignment adhesive polymerization emulsion comprises the following components in parts by weight:
further, the carboxyl modified polyvinyl alcohol is a mixture of carboxyl modified PVA21-88 and carboxyl modified PVA 21-93.
Further, the crosslinking agent is epichlorohydrin.
Further, the preparation method comprises the following steps:
(1) stirring and dissolving 13-14 parts by weight of carboxyl modified polyvinyl alcohol at 90-95 ℃ by using 253 parts by weight of deionized water containing 0.4-0.5 part by weight of defoaming agent in a reaction kettle, continuously keeping for about 60-70 minutes to completely dissolve the carboxyl modified polyvinyl alcohol, and then cooling to 75-77 ℃ and keeping.
(2) Uniformly mixing 99-101 parts by weight of vinyl acetate, 41-42 parts by weight of isooctyl acrylate, 36-37 parts by weight of vinyl versatate, 8.0-8.5 parts by weight of 2-hydroxyethyl acrylate and 2.0-2.1 parts by weight of acrylic acid to obtain a mixed monomer, and preparing 36-37 parts by weight of 1% hydrogen peroxide and 5.3-5.5 parts by weight of 10% tartaric acid.
(3) Adding 16-17 parts of 1% hydrogen peroxide and 5.3-5.5 parts of 10% tartaric acid into the reaction kettle at one time, simultaneously dropwise adding the mixed monomer obtained in the step (2), and synchronously dropwise adding the rest hydrogen peroxide after 50-55 minutes;
(4) controlling the mixed monomer in the step (2) to be dripped in 200-220 minutes, then dripping 4.0-4.5 parts by weight of epoxy chloropropane, controlling the dripping to be finished within 10-12 minutes, and controlling the hydrogen peroxide to be dripped in 210-220 minutes;
(5) after dropwise adding hydrogen peroxide, heating to 80-82 ℃ for 40-44 minutes, heating to 85-87 ℃ for 30-33 minutes, heating to 89-91 ℃ for 30-33 minutes, cooling to 60-62 ℃ and keeping;
(6) adding 4.0-4.5 parts by weight of calcium hydroxide, stirring for 60-65 minutes, cooling to below 45 ℃, adding 0.5-0.55 part by weight of preservative, and stirring for 20-25 minutes to obtain the environment-friendly plate alignment adhesive polymerization emulsion.
The invention has the beneficial effects that: the invention has the characteristics of no aldehyde, environmental protection, passing of a peeling rate test and high water resistance strength. According to the invention, epichlorohydrin is used as a crosslinking agent to replace an N-hydroxymethyl acrylamide monomer with formaldehyde release, and the monomer is crosslinked with carboxyl modified polyvinyl alcohol, acrylic acid-2-hydroxyethyl ester and acrylic acid with active functional groups in a polymerization system to form a macromolecular network structure, so that the water-resistant and heat-resistant properties are improved, and the problem of formaldehyde release is avoided. Although epichlorohydrin is considered to be a medium-toxicity substance, the active group of epichlorohydrin loses toxicity after the reaction, and the epichlorohydrin is environment-friendly. The carboxyl modified polyvinyl alcohol has stronger emulsifying capacity than common polyvinyl alcohol due to the existence of carboxyl, can reduce the dosage of the polyvinyl alcohol or other emulsifying agents (the dosage of the carboxyl modified polyvinyl alcohol is 2.6-2.8 percent, and the dosage of the common polyvinyl alcohol plus the emulsifying agent is 3.5-5.0 percent), and simultaneously, the crosslinking performance of the carboxyl is beneficial to improving the water resistance and the heat resistance when the polymerized emulsion is applied to the plate alignment adhesive.
Detailed Description
In order to make the purpose and technical scheme of the embodiment of the present invention clearer, the technical scheme of the embodiment of the present invention will be clearly described below, and the antifoaming agent and the preservative of the present invention are all conventional agents in the art.
Example one
(1) In a reaction kettle, using 250 parts by weight of deionized water containing 0.4 part by weight of defoaming agent, stirring and dissolving 10 parts by weight of carboxyl modified PVA21-88 and 3.5 parts by weight of carboxyl modified PVA21-93 at 90 ℃, keeping for 60 minutes to completely dissolve the materials, and then cooling to 75 ℃ and keeping.
(2) 100 parts by weight of vinyl acetate, 42 parts by weight of isooctyl acrylate, 36 parts by weight of vinyl versatate, 8.2 parts by weight of 2-hydroxyethyl acrylate and 2.0 parts by weight of acrylic acid are uniformly mixed to prepare 36 parts by weight of 1% hydrogen peroxide and 5.3 parts by weight of 10% tartaric acid.
(3) 16 parts by weight of 1% hydrogen peroxide and 5.3 parts by weight of 10% tartaric acid are added into the reaction kettle at one time, the mixed monomer is added dropwise at the same time, and after 50 minutes, the rest hydrogen peroxide is added dropwise at the same time.
(4) And controlling the mixed monomer to be dripped in 200 minutes, then dripping 4.2 parts by weight of epoxy chloropropane, controlling the mixed monomer to be dripped in 10 minutes, and controlling the hydrogen peroxide to be dripped in 210 minutes.
(5) After the dropwise addition of the hydrogen peroxide is finished, the temperature is increased to 80 ℃ and kept for 40 minutes, then the temperature is increased to 85 ℃ and kept for 30 minutes, then the temperature is increased to 90 ℃ and kept for 30 minutes, and then the temperature is reduced to 60 ℃ and kept.
(6) Adding 4.3 parts by weight of calcium hydroxide, stirring for 60 minutes, cooling to below 45 ℃, adding 0.5 part by weight of preservative, and stirring for 20 minutes to obtain the environment-friendly polymerization emulsion for the plate alignment adhesive.
Example two
(1) In a reaction kettle, 253 parts by weight of deionized water containing 0.4 part by weight of defoaming agent is stirred and dissolved at 90 ℃ for 11 parts by weight of carboxyl modified PVA21-88 and 3 parts by weight of carboxyl modified PVA21-93, the mixture is kept for 60 minutes to be completely dissolved, and then the temperature is reduced to 77 ℃ and maintained.
(2) 99 parts by weight of vinyl acetate, 41 parts by weight of isooctyl acrylate, 36 parts by weight of vinyl versatate, 8.0 parts by weight of 2-hydroxyethyl acrylate and 2.1 parts by weight of acrylic acid are mixed uniformly to prepare 37 parts by weight of 1% hydrogen peroxide and 5.4 parts by weight of 10% tartaric acid.
(3) Adding 17 parts by weight of 1% hydrogen peroxide and 5.4 parts by weight of 10% tartaric acid into the reaction kettle at one time, simultaneously beginning to dropwise add the mixed monomer, and after 50 minutes, synchronously dropwise adding the rest hydrogen peroxide.
(4) And controlling the mixed monomer to be dripped in 200 minutes, then dripping 4.0 parts by weight of epoxy chloropropane, controlling the mixed monomer to be dripped in 10 minutes, and controlling the hydrogen peroxide to be dripped in 210 minutes.
(5) After the dropwise addition of the hydrogen peroxide is finished, the temperature is increased to 80 ℃ and kept for 40 minutes, then the temperature is increased to 85 ℃ and kept for 30 minutes, then the temperature is increased to 90 ℃ and kept for 30 minutes, and then the temperature is reduced to 60 ℃ and kept.
(6) Adding 4.0 parts by weight of calcium hydroxide, stirring for 60 minutes, cooling to below 45 ℃, adding 0.55 part by weight of preservative, and stirring for 20 minutes to obtain the environment-friendly polymerized emulsion for the plate alignment adhesive.
EXAMPLE III
(1) In a reaction kettle, using 250 parts by weight of deionized water containing 0.5 part by weight of defoaming agent, stirring and dissolving 11 parts by weight of carboxyl modified PVA21-88 and 2 parts by weight of carboxyl modified PVA21-93 at 90 ℃, keeping for 60 minutes to completely dissolve the materials, and then cooling to 76 ℃ and keeping.
(2) 101 parts by weight of vinyl acetate, 42 parts by weight of isooctyl acrylate, 37 parts by weight of vinyl versatate, 8.5 parts by weight of 2-hydroxyethyl acrylate and 2.1 parts by weight of acrylic acid are uniformly mixed to prepare 36 parts by weight of 1% hydrogen peroxide and 5.3 parts by weight of 10% tartaric acid.
(3) 16 parts by weight of 1% hydrogen peroxide and 5.3 parts by weight of 10% tartaric acid are added into the reaction kettle at one time, the mixed monomer is added dropwise at the same time, and after 50 minutes, the rest hydrogen peroxide is added dropwise at the same time.
(4) And controlling the mixed monomer to be dripped in 200 minutes, then dripping 4.5 parts by weight of epoxy chloropropane, controlling the mixed monomer to be dripped in 10 minutes, and controlling the hydrogen peroxide to be dripped in 210 minutes.
(5) After the dropwise addition of the hydrogen peroxide is finished, the temperature is increased to 80 ℃ and kept for 40 minutes, then the temperature is increased to 85 ℃ and kept for 30 minutes, then the temperature is increased to 90 ℃ and kept for 30 minutes, and then the temperature is reduced to 60 ℃ and kept.
(6) Adding 4.5 parts by weight of calcium hydroxide, stirring for 60 minutes, cooling to below 45 ℃, adding 0.5 part by weight of preservative, and stirring for 20 minutes to obtain the environment-friendly polymerization emulsion for the plate alignment adhesive.
The detection results of several conventional physicochemical indexes of 3 examples and 2 market competitive products are shown in the following table:
in order to compare and evaluate the performances of the plate alignment adhesive polymerization emulsion and 2 market competitive product emulsions obtained in the above 3 examples, the following experiments were carried out: 144 parts of polymerization emulsion, 80 parts of calcium powder of 1250 meshes, 60 parts of 15% PVA24-88 solution, 0.3 part of dispersing agent, 0.3 part of wetting agent, 16 parts of water, 0.3 part of defoaming agent and 0.3 part of preservative by weight, stirring for 30 minutes, and adjusting the viscosity to 12000 +/-2000 mPa & s by using appropriate amount of water to obtain the 5-two-component main agent of the plate alignment adhesive. Respectively mixing 5 main agents and an isocyanate curing agent according to the weight ratio of 100: 15, uniformly mixing, splicing beech, pressurizing for 24 hours for pressure relief, after curing for 72 hours, carrying out comparison verification according to a daily JAS111 structural integrated material water-resistant impregnation performance test (stripping rate), and obtaining the following results:
| sample (I) | Boiling in boiling water for 4h, soaking in cold water for 1h, and drying in an oven at 70 +/-3 ℃ for 24 h; was subjected to 2 cycles | The stripping rate is less than or equal to 5 percent |
| Competition 1 | The peeling rate is 2.0 percent | Reach the standard |
| Competition 2 | The peeling rate is more than 20 percent | Does not reach the standard |
| Example 1 | The peeling rate is 1.0% | Reach the standard |
| Example 2 | The peeling rate is 3.0 percent | Reach the standard |
| Example 3 | The peeling rate was 0% | Reach the standard |
The comparison and detection prove that the market competitive product polymerized emulsion often has the phenomenon that free formaldehyde or the stripping rate does not reach the standard, and the environment-friendly plate alignment adhesive polymerized emulsion provided by the invention reaches the ten-ring standard in the environmental protection property of the free formaldehyde and also reaches the standard in the stripping rate reflecting the water-resistant and heat-resistant properties. The reason why the peeling rate is lower (more effective) than that in example 2 in example 3 is that the water-resistant and heat-resistant properties are improved by using a slightly larger amount of epichlorohydrin and a slightly smaller amount of the carboxyl group-modified polyvinyl alcohol.
Claims (4)
1. The environment-friendly plate alignment adhesive polymerization emulsion is characterized by comprising the following components in parts by weight:
2. the environmentally friendly jigsaw puzzle glue polymerization emulsion of claim 1, wherein the carboxyl modified polyvinyl alcohol is a mixture of carboxyl modified PVA21-88 and carboxyl modified PVA 21-93.
3. The environmentally friendly jigsaw puzzle polymer emulsion of claim 1, wherein the crosslinking agent is epichlorohydrin.
4. The environment-friendly plate alignment adhesive polymerization emulsion as defined in claim 1, which is prepared by the following process method:
(1) stirring and dissolving 13-14 parts by weight of carboxyl modified polyvinyl alcohol at 90-95 ℃ by using 253 parts by weight of deionized water containing 0.4-0.5 part by weight of defoaming agent in a reaction kettle, continuously keeping for about 60-70 minutes to completely dissolve the carboxyl modified polyvinyl alcohol, and then cooling to 75-77 ℃ and keeping.
(2) Uniformly mixing 99-101 parts by weight of vinyl acetate, 41-42 parts by weight of isooctyl acrylate, 36-37 parts by weight of vinyl versatate, 8.0-8.5 parts by weight of 2-hydroxyethyl acrylate and 2.0-2.1 parts by weight of acrylic acid to obtain a mixed monomer, and preparing 36-37 parts by weight of 1% hydrogen peroxide and 5.3-5.5 parts by weight of 10% tartaric acid.
(3) Adding 16-17 parts of 1% hydrogen peroxide and 5.3-5.5 parts of 10% tartaric acid into the reaction kettle at one time, simultaneously dropwise adding the mixed monomer obtained in the step (2), and synchronously dropwise adding the rest hydrogen peroxide after 50-55 minutes;
(4) controlling the mixed monomer in the step (2) to be dripped in 200-220 minutes, then dripping 4.0-4.5 parts by weight of epoxy chloropropane, controlling the dripping to be finished within 10-12 minutes, and controlling the hydrogen peroxide to be dripped in 210-220 minutes;
(5) after dropwise adding hydrogen peroxide, heating to 80-82 ℃ for 40-44 minutes, heating to 85-87 ℃ for 30-33 minutes, heating to 89-91 ℃ for 30-33 minutes, cooling to 60-62 ℃ and keeping;
(6) adding 4.0-4.5 parts by weight of calcium hydroxide, stirring for 60-65 minutes, cooling to below 45 ℃, adding 0.5-0.55 part by weight of preservative, and stirring for 20-25 minutes to obtain the environment-friendly plate alignment adhesive polymerization emulsion.
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| CN202110709685.7A CN113461853A (en) | 2021-06-25 | 2021-06-25 | Environment-friendly plate alignment adhesive polymerization emulsion and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461785A (en) * | 2002-05-30 | 2003-12-17 | 株式会社大鹿 | Water-resistant adhesive composite for wood |
| CN103709971A (en) * | 2013-12-04 | 2014-04-09 | 台州市顶立胶粘剂有限公司 | Emulsion for bi-component wood bonding adhesive and synthesis method thereof |
| CN104629658A (en) * | 2015-01-22 | 2015-05-20 | 浙江农林大学 | Non-formaldehyde starch-base vinyl acetate adhesive production method |
| CN105754524A (en) * | 2016-02-29 | 2016-07-13 | 广西大学 | Preparation method for corn starch based wood adhesive |
| CN110872362A (en) * | 2018-08-31 | 2020-03-10 | 中国石油化工股份有限公司 | Vinyl acetate-ethylene copolymer emulsion and preparation method thereof |
| CN111087943A (en) * | 2018-10-24 | 2020-05-01 | 江门市金桥新材料有限公司 | Modified starch adhesive |
-
2021
- 2021-06-25 CN CN202110709685.7A patent/CN113461853A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461785A (en) * | 2002-05-30 | 2003-12-17 | 株式会社大鹿 | Water-resistant adhesive composite for wood |
| CN103709971A (en) * | 2013-12-04 | 2014-04-09 | 台州市顶立胶粘剂有限公司 | Emulsion for bi-component wood bonding adhesive and synthesis method thereof |
| CN104629658A (en) * | 2015-01-22 | 2015-05-20 | 浙江农林大学 | Non-formaldehyde starch-base vinyl acetate adhesive production method |
| CN105754524A (en) * | 2016-02-29 | 2016-07-13 | 广西大学 | Preparation method for corn starch based wood adhesive |
| CN110872362A (en) * | 2018-08-31 | 2020-03-10 | 中国石油化工股份有限公司 | Vinyl acetate-ethylene copolymer emulsion and preparation method thereof |
| CN111087943A (en) * | 2018-10-24 | 2020-05-01 | 江门市金桥新材料有限公司 | Modified starch adhesive |
Non-Patent Citations (2)
| Title |
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| 杨猛等: "一种高强度双组分拼板胶PVAc乳液的制备", 《当代化工》 * |
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