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CN112920744B - Amino acid modified polyvinyl alcohol efficient composite adhesive and preparation method and application thereof - Google Patents

Amino acid modified polyvinyl alcohol efficient composite adhesive and preparation method and application thereof Download PDF

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CN112920744B
CN112920744B CN202110108296.9A CN202110108296A CN112920744B CN 112920744 B CN112920744 B CN 112920744B CN 202110108296 A CN202110108296 A CN 202110108296A CN 112920744 B CN112920744 B CN 112920744B
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polyvinyl alcohol
amino acid
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modified polyvinyl
acid modified
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CN112920744A (en
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郑自勇
郑凯森
石通秀
孙哲
王公友
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Lanling Jason Decoration Materials Co ltd
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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
    • C09J129/00—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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses an amino acid modified polyvinyl alcohol efficient composite adhesive as well as a preparation method and application thereof, belonging to the technical field of functional polymer materials; the adhesive is prepared by uniformly stirring and mixing amino acid modified polyvinyl alcohol (PVA-g-AA), a viscosity modifier, a dispersant, a defoaming agent, a filler and water in parts by mass; wherein, the amino acid modified polyvinyl alcohol is prepared by the esterification reaction of carboxyl in an amino acid structure and hydroxyl in a polyvinyl alcohol structure; the amino acid monomer type is screened, the amino acid monomer and polyvinyl alcohol ratio are regulated and controlled to prepare a series of amino acid modified polyvinyl alcohol, and then a series of amino acid modified polyvinyl alcohol high-efficiency composite adhesives are prepared by assisting with a functional auxiliary agent and a filler; the result shows that the amino acid modified polyvinyl alcohol efficient composite adhesive prepared by the invention is green and environment-friendly, has no aldehyde, is further used for producing multilayer artificial boards, and the obtained products have good water resistance and weather resistance and large bonding strength, so that the application prospect is wide.

Description

Amino acid modified polyvinyl alcohol efficient composite adhesive and preparation method and application thereof
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to an amino acid modified polyvinyl alcohol efficient composite adhesive as well as a preparation method and application thereof.
Background
The artificial board industry in China keeps a high-speed development trend, and the yield accounts for more than 60% of the yield of the artificial boards in the world by 2017, so that the artificial board industry becomes a super large country of the artificial boards which draw attention in the world. Huge artificial board output inevitably needs a large amount of adhesives, and according to relevant data, the usage amount of the industrial adhesives of the artificial boards in China in 2015 is up to 1530 ten thousand tons, and the usage amount of the industrial adhesives accounts for about 87.8% of the usage amount of the adhesives of the wood in China. At present, most of adhesives for the artificial board industry in China are synthetic resin adhesives, wherein aldehyde adhesives (formaldehyde-formaldehyde adhesives, urea-formaldehyde resin adhesives, phenol-formaldehyde resin adhesives and melamine urea-formaldehyde resin adhesives) are most widely applied, and can release harmful substances such as free formaldehyde and the like in the production and use processes to pollute air and bring great harm to production and life of people.
Research shows that modern people spend 80% of the time indoors, and the health of human living environment is more and more emphasized. The national standard of China, namely Formaldehyde release limit in interior decoration and finishing material artificial boards and products thereof (GB18580-2017), is implemented in 2018, and puts more stringent requirements on formaldehyde release of artificial boards and products thereof; meanwhile, home decoration products (such as children furniture, hospital furniture, geothermal floors and the like)) in some special places and sensitive people have strong demand on manufacturing the artificial board by adding the adhesive without formaldehyde, so that the artificial board industry leading by the aldehyde resin adhesive is seriously challenged, and how to reduce and eliminate formaldehyde release of the artificial board becomes a research hotspot of the artificial board industry. At present, the aldehyde-free adhesives for artificial boards popularized in the market mainly comprise water-based polymer/isocyanate wood Adhesives (API), modified soy protein adhesives, polymethylene polyphenyl Polyisocyanate (PMDI), modified thermoplastic films and the like. In fact, the realization of large-scale general popularization of certain types of aldehyde-free glue in the artificial board processing industry of China still has a plurality of difficulties, such as poor process applicability, high cost, no product competitiveness and the like. Therefore, the research on the hydroformylation-free key technology of the adhesive for the artificial board has practical significance.
Among them, polyvinyl alcohol (PVA) is a water-soluble polymer with very wide applications, and has been used in the production of a large number of products such as coatings, emulsifiers, adhesives, textiles, paper processing agents, plastic films, and the like. PVA has good adhesion, is colorless and transparent, has high adhesive film strength, and has the features of simple production process, fast curing speed, solvent resistance, etc. However, the polyvinyl alcohol glue has low solid content and poor water resistance, and the application of the polyvinyl alcohol glue in the aspect of artificial boards is limited. In order to meet the application requirements of the field of artificial boards, the artificial boards need to be modified, the modification method mainly comprises copolymerization modification, blending modification and post-polymer reaction (related to etherification, acetalation, crosslinking, degradation, surface modification and the like), and the performance of polyvinyl alcohol can be optimized and the application field of the polyvinyl alcohol can be widened through modification. Therefore, the invention utilizes a simple strategy, namely utilizes the reactivity of a polyvinyl alcohol structure containing a large amount of free hydroxyl groups to carry out grafting reaction with amino acid monomers to prepare the amino acid modified polyvinyl alcohol, and utilizes polar groups, alicyclic or aromatic ring structures and the like in amino acid molecules to improve the water resistance, weather resistance, bonding strength and other properties of the polyvinyl alcohol.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide an amino acid modified polyvinyl alcohol efficient composite adhesive.
The invention also aims to provide a preparation method of the amino acid modified polyvinyl alcohol efficient composite adhesive.
The invention also aims to provide application of the amino acid modified polyvinyl alcohol high-efficiency composite adhesive in the fields of wood bonding and deep processing of laminated boards, laminated wood boards, low-medium density fiberboards, shaving boards and the like.
In order to solve the problems in the prior art and achieve the technical purpose of the invention, the invention starts with the design and preparation of a polymer molecular structure based on an aldehyde-free adhesive design concept, takes an amino acid monomer (AA) as a modifier to carry out structural modification on polyvinyl alcohol (PVA), prepares a series of amino acid modified polyvinyl alcohol (PVA-g-AA) by screening the types of the amino acid monomer (AA) and regulating the proportion of the amino acid monomer (AA) and the polyvinyl alcohol (PVA), and then prepares a series of amino acid modified polyvinyl alcohol high-efficiency composite adhesives by assisting a functional assistant and a filler. The result shows that the amino acid modified polyvinyl alcohol high-efficiency composite adhesive prepared by the invention is environment-friendly, free of aldehyde, good in water resistance and weather resistance, and high in bonding strength, is further used for plywood production, and has product performance completely meeting the technical indexes of class II boards of GB/T17657-2013GB/T17657-2013 test methods for physical and chemical properties of artificial boards and decorative artificial boards, and wide application prospect.
Specifically, the technical scheme adopted by the invention is as follows:
an amino acid modified polyvinyl alcohol efficient composite adhesive is composed of 20-60 parts of amino acid modified polyvinyl alcohol (PVA-g-AA), 3-7 parts of an adhesive, 0.5-1.2 parts of a dispersing agent, 0.5-1 part of a defoaming agent, 20-40 parts of a filler and 40-60 parts of water, and the components are calculated according to the parts by weight:
the preparation method of the amino acid modified polyvinyl alcohol efficient composite adhesive comprises the following steps: adding the amino acid modified polyvinyl alcohol and the viscosity modifier into deionized water at room temperature according to the formula proportion, stirring for 10-15 min, adding a dispersing agent, a defoaming agent and a filler, and continuously stirring for 10-15 min to obtain the amino acid modified polyvinyl alcohol efficient composite adhesive;
the amino acid modified polyvinyl alcohol (PVA-g-AA) is prepared by esterification reaction of functional carboxylic acid groups (COOH) in an Amino Acid (AA) structure and functional hydroxyl groups (OH) in a polyvinyl alcohol (PVA) structure;
the preparation reaction formula of the amino acid modified polyvinyl alcohol (PVA-g-AA) is shown as a formula 1, and the preparation method comprises the following steps:
putting polyvinyl alcohol (PVA) into a reaction kettle, adding N, N-Dimethylformamide (DMF), heating to 70 ℃ to completely dissolve the PVA, adding concentrated sulfuric acid to adjust the pH value of the solution to be weak acid (3-4), adding an amino acid monomer (AA), heating to 90-100 ℃ to react for 8-12 h, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol (PVA-g-AA).
Figure BDA0002918365120000031
The amino acid monomer (AA) comprises glycine, alanine, serine, threonine, lysine, glutamine, asparagine, proline, histidine and tyrosine, the structural formula is shown as a formula 2, wherein threonine, lysine, proline, histidine and tyrosine are preferably selected;
Figure BDA0002918365120000032
the polyvinyl alcohol (PVA) has a chemical formula of (C) 2 H 4 O) n The average molecular weight is 16000-200000, and the types of commercial polyvinyl alcohol (PVA) are 1788, 1799,2099, 2488, 2499; preferred commercially available polyvinyl alcohol (PVA) models are 1788 (degree of polymerization 1700, degree of alcoholysis 88%) and 2488 (degree of polymerization 2400, degree of alcoholysis 88%);
the charging ratio of the amino acid monomer (AA) and the polyvinyl alcohol (PVA) is calculated according to the molar ratio of Carboxyl (COOH) in the amino acid monomer (AA) to hydroxyl (OH) in the polyvinyl alcohol (PVA) (M COOH :M OH ) Preferably, the feeding ratio is 1: 0.3-1: 1;
the viscosity modifier is cellulose and starch, preferably one or more of hydroxypropyl methyl cellulose ether, pregelatinized starch, sodium carboxymethyl starch and sodium carboxymethyl cellulose;
the dispersant is inorganic dispersant and organic dispersant, preferably one or more of sodium tripolyphosphate, sodium hexametaphosphate, sodium citrate and polycarboxylic acid dispersant;
the defoaming agent is one or more of a mineral oil defoaming agent, a polyether defoaming agent, an organic silicon defoaming agent and a polyether modified organic silicon defoaming agent;
the filler is one or more of 800-1200 mesh quartz sand, coarse whiting, wollastonite powder, kaolin, bentonite and montmorillonite;
the application of the amino acid modified polyvinyl alcohol efficient composite adhesive is in the fields of wood bonding and deep processing such as laminated boards, laminated wood boards, low-medium density fiberboard, shaving boards and the like.
The application of the amino acid modified polyvinyl alcohol high-efficiency composite adhesive designed and prepared by the invention has the following advantages and beneficial effects:
(1) the amino acid modified polyvinyl alcohol efficient composite adhesive prepared by the invention takes water as a solvent, and is green and environment-friendly; meanwhile, formaldehyde is not involved, so that no hydroformylation of the adhesive used in the field of wood processing is really realized.
(2) The amino acid modified polyvinyl alcohol high-efficiency composite adhesive prepared by the invention introduces an environment-friendly amino acid monomer, and improves the water resistance, weather resistance and bonding strength of the polyvinyl alcohol adhesive by utilizing polar groups, alicyclic or aromatic ring structures and the like in the molecular structure of the amino acid.
(3) The amino acid modified polyvinyl alcohol high-efficiency composite adhesive prepared by the invention has simple process and is environment-friendly; by optimally regulating and controlling the proportion and the composition of the raw materials, the application requirements of different wood processing fields such as laminated boards, laminated wood boards, low-medium density fiberboards, shaving boards and the like which are molded under various pressures and hot pressing can be met, and the application prospect is wide.
Detailed Description
The technical solutions of the present invention are further described below with reference to specific examples, examples 1 to 15 are preparation of amino acid modified polyvinyl alcohol (PVA-g-AA), and examples 16 to 36 are preparation of amino acid modified polyvinyl alcohol efficient composite adhesives, but the embodiments of the present invention are not limited thereto.
Example 1
Putting 10 parts of polyvinyl alcohol (1788) into a reaction kettle, adding 80 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (pH is 3-4), adding 24 parts of threonine, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 2
Putting 10 parts of polyvinyl alcohol (1788) into a reaction kettle, adding 50 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (pH is 3-4), adding 29 parts of lysine, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 3
Putting 10 parts of polyvinyl alcohol (1788) into a reaction kettle, adding 80 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (pH is 3-4), adding 23 parts of proline, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 4
Putting 10 parts of polyvinyl alcohol (1788) into a reaction kettle, adding 80 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (pH is 3-4), adding 31 parts of histidine, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 5
Putting 10 parts of polyvinyl alcohol (1788) into a reaction kettle, adding 80 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (the pH value is 3-4), adding 36 parts of tyrosine, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 6
Putting 10 parts of polyvinyl alcohol (2488) into a reaction kettle, adding 80 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (pH is 3-4), adding 27 parts of threonine, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 7
Putting 10 parts of polyvinyl alcohol (2488) into a reaction kettle, adding 50 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (pH is 3-4), adding 33 parts of lysine, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 8
Putting 10 parts of polyvinyl alcohol (2488) into a reaction kettle, adding 80 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (pH is 3-4), adding 26 parts of proline, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 9
Putting 10 parts of polyvinyl alcohol (2488) into a reaction kettle, adding 80 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (pH is 3-4), adding 35 parts of histidine, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 10
Putting 10 parts of polyvinyl alcohol (2488) into a reaction kettle, adding 80 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (the pH value is 3-4), adding 41 parts of tyrosine, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 11
Putting 10 parts of polyvinyl alcohol (1788) into a reaction kettle, adding 50 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (pH is 3-4), adding 10 parts of lysine, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 12
Putting 10 parts of polyvinyl alcohol (1788) into a reaction kettle, adding 80 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (pH is 3-4), adding 12 parts of proline, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 13
Putting 10 parts of polyvinyl alcohol (2488) into a reaction kettle, adding 80 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (pH is 3-4), adding 9 parts of threonine, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 14
Putting 10 parts of polyvinyl alcohol (2488) into a reaction kettle, adding 50 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (pH is 3-4), adding 17 parts of lysine, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 15
Putting 10 parts of polyvinyl alcohol (2488) into a reaction kettle, adding 80 parts of N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, adding concentrated sulfuric acid to adjust the solution to be weakly acidic (the pH value is 3-4), adding 21 parts of tyrosine, heating to 90-100 ℃ to react for 8-12 hours, precipitating with acetone after the reaction is finished, and filtering to obtain the amino acid modified polyvinyl alcohol.
Example 16
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 1 and 5 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 17
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 2 and 5 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the deionized water, and stirring is continued for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 18
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the embodiment 3 and 5 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 19
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the embodiment 4 and 5 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the deionized water, and stirring is continued for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 20
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 5 and 5 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 21
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 6 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 22
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 7 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 23
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the embodiment 8 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the deionized water, and stirring is continued for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 24
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 9 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the deionized water, and stirring is continued for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 25
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 10 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 26
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the embodiment 11 and 5 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the deionized water, and stirring is continued for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 27
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 12 and 5 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the deionized water, and stirring is continued for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 28
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 13 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 29
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 14 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 30
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 15 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 30
According to the formula proportion, 30 parts of the amino acid modified polyvinyl alcohol prepared in the example 2 and 4 parts of a tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of a dispersing agent, 0.8 part of a defoaming agent and 10 parts of a filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 31
According to the formula proportion, 20 parts of the amino acid modified polyvinyl alcohol prepared in the example 7 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.9 part of dispersing agent, 0.8 part of defoaming agent and 20 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 32
According to the formula proportion, 30 parts of the amino acid modified polyvinyl alcohol prepared in the embodiment 3 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 10 parts of filler are added into the deionized water, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 33
According to the formula proportion, 20 parts of the amino acid modified polyvinyl alcohol prepared in the example 8 and 3 parts of a tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.9 part of a dispersing agent, 0.8 part of a defoaming agent and 20 parts of a filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 33
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 12 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 34
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 5 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 35
According to the formula proportion, 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 10 and 3 parts of the tackifier are added into 60 parts of deionized water at room temperature, stirred for 10-15 min, then 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler are added into the mixture, and the mixture is continuously stirred for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
Example 36
Adding 25 parts of the amino acid modified polyvinyl alcohol prepared in the example 15 and 3 parts of a tackifier into 60 parts of deionized water at room temperature, stirring for 10-15 min, adding 0.6 part of a dispersing agent, 0.8 part of a defoaming agent and 15 parts of a filler, and continuously stirring for 10-15 min to obtain the amino acid modified polyvinyl alcohol efficient composite adhesive.
Comparative example 1
Adding 25 parts of polyvinyl alcohol (1788) and 3 parts of tackifier into 60 parts of deionized water at room temperature, stirring for 10-15 min, then adding 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler, and continuously stirring for 10-15 min to obtain the amino acid modified polyvinyl alcohol efficient composite adhesive.
Comparative example 2
Adding 25 parts of polyvinyl alcohol (2488) and 3 parts of tackifier into 60 parts of deionized water at room temperature, stirring for 10-15 min, then adding 0.6 part of dispersing agent, 0.8 part of defoaming agent and 15 parts of filler, and continuously stirring for 10-15 min to obtain the amino acid modified polyvinyl alcohol efficient composite adhesive.
Adhesive performance test one
The appearance, stability and formaldehyde emission of the amino acid modified polyvinyl alcohol high-efficiency composite adhesive prepared by the invention are measured, and the results are shown in table 1. The table shows that the amino acid modified polyvinyl alcohol efficient composite adhesive prepared by the invention has excellent performances in the aspects of appearance, sizing performance and formaldehyde content.
TABLE 1 physicochemical Properties of the Adhesives of the comparative examples (1 and 2) and of the examples according to the invention (16 to 36)
Figure BDA0002918365120000101
Preparation and performance test of multilayer artificial board II
The amino acid modified polyvinyl alcohol high-efficiency composite adhesive prepared by the invention is used for preparing a multilayer artificial board, and the production process of the multilayer artificial board comprises the following steps: firstly, the adhesive prepared by the invention is coated on a veneer by a double-sided coating method (the coating amount is controlled to be 200 g/m) 2 And left and right), assembling the glued single boards according to the required board area and the number of single-layer boards to obtain board blanks, then placing the prepared board blanks into a press to perform cold press molding and hot press molding respectively, and finally performing pressure relief and edge sawing and sanding respectively to obtain finished products of the multilayer artificial boards.
The performance of the multilayer artificial board prepared by the amino acid modified polyvinyl alcohol high-efficiency composite adhesive is determined according to II-type board technical indexes specified in standards such as GB/T17657-2013 test methods for physical and chemical properties of artificial boards and veneered artificial boards, GB/T15104-2006 veneered artificial boards for decorative veneers, GB18580-2001 limit of formaldehyde release in artificial boards and products thereof for interior decoration and finishing materials, and the like. The results are shown in Table 2. As can be seen from the table, the multilayer artificial board prepared based on the amino acid modified polyvinyl alcohol high-efficiency composite adhesive has excellent bonding strength, and meanwhile, the water resistance of the multilayer artificial board is also obviously improved; in addition, no formaldehyde residue is detected, so that the amino acid modified polyvinyl alcohol high-efficiency composite adhesive has wide application prospect.
TABLE 2 Properties of comparative examples (1 and 2) and of Adhesives applied in examples (16-36) of the invention to produce Multi-layered Wood-based Panel
Figure BDA0002918365120000111
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. It is obvious that the above-mentioned embodiments of the present invention, and all other embodiments obtained by those skilled in the art without making creative efforts, shall fall within the protection scope of the present invention.

Claims (4)

1. The amino acid modified polyvinyl alcohol efficient composite adhesive is characterized by comprising 20-30 parts of amino acid modified polyvinyl alcohol, 3-7 parts of an adhesive, 0.5-1.2 parts of a dispersing agent, 0.5-1 part of a defoaming agent, 15-20 parts of a filler and 40-60 parts of water, wherein the components are calculated according to parts by weight;
the amino acid modified polyvinyl alcohol is prepared by performing esterification reaction on functional carboxylic acid groups in an amino acid structure and functional hydroxyl groups in a polyvinyl alcohol structure;
the amino acids include glycine, alanine, serine, threonine, lysine, glutamine, asparagine, proline, histidine and tyrosine;
the polyvinyl alcohol has a chemical formula of (C) 2 H 4 O) n The average molecular weight is 16000-200000, and the types of the commercial polyvinyl alcohol are 1788, 1799, 2099, 2488 and 2499;
the preparation method of the amino acid modified polyvinyl alcohol comprises the following steps: putting polyvinyl alcohol into a reaction kettle, adding N, N-dimethylformamide, heating to 70 ℃ to completely dissolve the polyvinyl alcohol, then adding concentrated sulfuric acid to adjust the pH of the solution to 3-4, then adding amino acid, heating to 90-100 ℃ to react for 8-12 h, and after the reaction is finished, precipitating with acetone and filtering to obtain the amino acid modified polyvinyl alcohol.
2. The amino acid modified polyvinyl alcohol high-efficiency composite adhesive as claimed in claim 1, wherein the viscosity modifier is one or more of hydroxypropyl methyl cellulose ether, pregelatinized starch, sodium carboxymethyl starch and sodium carboxymethyl cellulose;
the dispersing agent is one or more of sodium tripolyphosphate, sodium hexametaphosphate, sodium citrate and polycarboxylic acid dispersing agent;
the defoaming agent is one or more of a mineral oil defoaming agent, a polyether defoaming agent, an organic silicon defoaming agent and a polyether modified organic silicon defoaming agent;
the filler is one or more of 800-1200 mesh quartz sand, coarse whiting, wollastonite powder, kaolin, bentonite and montmorillonite.
3. The preparation method of the amino acid modified polyvinyl alcohol efficient composite adhesive according to any one of claims 1 to 2, wherein the amino acid modified polyvinyl alcohol and the viscosity modifier are added into deionized water at room temperature, stirred for 10-15 min, then a dispersant, a defoamer and a filler are added into the deionized water, and stirring is continued for 10-15 min, so that the amino acid modified polyvinyl alcohol efficient composite adhesive is obtained.
4. The application of the amino acid modified polyvinyl alcohol efficient composite adhesive as claimed in any one of claims 1 to 2 is characterized in that the adhesive is applied to the fields of gluing and deep processing of laminated boards, core-board boards, low-medium density fiber boards and shaving boards.
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