WO2017118173A1 - Formaldehyde-free adhesive and method for preparing same - Google Patents

Formaldehyde-free adhesive and method for preparing same Download PDF

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Publication number
WO2017118173A1
WO2017118173A1 PCT/CN2016/103621 CN2016103621W WO2017118173A1 WO 2017118173 A1 WO2017118173 A1 WO 2017118173A1 CN 2016103621 W CN2016103621 W CN 2016103621W WO 2017118173 A1 WO2017118173 A1 WO 2017118173A1
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Prior art keywords
density polyethylene
ethylene
low density
grafted
acrylic acid
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PCT/CN2016/103621
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French (fr)
Chinese (zh)
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郑玉婴
肖东升
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福州大学
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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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/06—Polyethene
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • 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
    • C09J151/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Definitions

  • the invention belongs to the field of preparation of adhesives, in particular to an aldehyde-free adhesive and a preparation method thereof.
  • the thermoplastic resin plywood is made of a thermoplastic resin film as a bonding material, which is convenient for cleaning and eliminates formaldehyde pollution. It is a promising aldehyde-free plywood product, which is particularly suitable for traditional Plywood enterprise product update and upgrade.
  • wood is a non-uniform anisotropic material, it is composed of cellulose, hemicellulose, lignin, and extracts containing a large amount of polar hydroxyl groups and phenolic hydroxyl functional groups, and exhibits strong chemical polarity.
  • hydrophilicity when it is glued with non-polar thermoplastic resin, such as HDPE film, the interface bonding force is weak, and the boiling water resistance is poor, which greatly limits the application range of the material.
  • the preparation of the polymer composite film to improve the compatibility and bonding force with the wood raw material as a binder is a relatively simple and effective method for improving the interfacial compatibility and strength of the thermoplastic resin plywood.
  • the polymer composite film is placed between the veneers, and the plywood bundles are first placed on a hot press for heating and pressurization, and then moved to a cold press for pressurization and cooling.
  • a novel aldehyde-free plywood is obtained, which has the characteristics of good mechanical properties, no formaldehyde release, and has wide social benefits.
  • the object of the present invention is to provide a novel aldehyde-free adhesive and a preparation method thereof for the deficiencies of the conventional plywood products.
  • the use of the aldehyde-free adhesive to prepare plywood can improve the compatibility and bonding force of the adhesive and the wood raw material, and has no formaldehyde release, good mechanical properties and wide social benefits.
  • the present invention adopts the following technical solutions:
  • an aldehyde-free adhesive wherein the aldehyde-free adhesive is a polymer composite film; the raw material composition is: by weight: 100 parts of the resin, 15-25 parts of the graft; the graft is high density Polyethylene grafted acrylic acid (grafting rate 15.9%), low density polyethylene grafted acrylic acid (grafting rate 8.5%), ethylene-vinyl acetate copolymer grafted acrylic acid (grafting rate 11.1%), linear low density polyethylene Grafted acrylic acid (grafting rate 2.7%), ethylene-octene copolymer grafted acrylic acid (grafting rate 5.4%) (all of which are self-made), high density polyethylene grafted maleic anhydride, low density polyethylene grafted Maleic anhydride, linear low density polyethylene grafted maleic anhydride (supplied from Nanjing Juxing Polymer Co., Ltd.), ethylene-octene copolymer grafted maleic anhydride, ethylene-vinyl acetate copolymer graf
  • the aldehyde-free adhesive is prepared by thoroughly mixing the resin and the graft in a blast drying oven, drying at 40 to 60 ° C for 5 to 7 hours, and adding the mixed material to the extrusion blown film machine or the casting machine. Film formation was carried out to obtain a polymer composite film.
  • the screw temperatures are: 175 to 185 ° C for the die, 170 to 180 ° C for the three-way segment, and 160 to 170 ° C for the third segment, and the second. Section 155 ⁇ 165 ° C, feed section 145 ⁇ 155 ° C.
  • the aldehyde-free adhesive as described above is applied to the plywood: the polymer composite film is laid between the veneers, and the plywood bundle is first placed on a hot press to be heated and pressurized, and then moved to a cold press for pressurization. Cooling; the hot pressing temperature on the hot press is 140-170 ° C, the hot pressing pressure is 0.7-1.0 MPa, the hot pressing time is 300-500 s; the cold pressing pressure on the cold press is 0.7-1.1 MPa, cold pressing time It is 400s to 600s.
  • the novel aldehyde-free adhesive obtained by the invention can improve the compatibility and bonding force of the adhesive and the wood raw material when preparing the plywood, and has no formaldehyde release, good mechanical property, convenient production and cleaning, and the plywood meets the national standard GB. /T17657-2013 "Experimental Methods for Physical and Chemical Properties of Artificial Panels and Finished Panels" A standard for the bonding strength of a class of plywood, and no formaldehyde release, the strength reaches a class of board standards;
  • step 2) The material mixed in the step 1) is added to an extrusion blown film machine to form a film, and a polymer composite film is obtained; wherein the screw temperatures are: 185 ° C, 180 ° C, 165 ° C, 155 ° C, 145 ° C;
  • the polymer composite film prepared in the step 2) is laid between the veneers, and the plywood bundle is first placed on a hot press to be heated and pressurized, and then moved to a cold press for pressurization and cooling;
  • the hot pressing temperature is 150 ° C
  • the hot pressing pressure is 0.7 MPa
  • the hot pressing time is 400 s
  • the cold pressing pressure is 0.8 MPa
  • the cold pressing time is 500 s.
  • step 2) The material mixed in the step 1) is added to a casting machine to form a film, and a polymer composite film is obtained; wherein the screw temperatures are: 180 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C, respectively. ;
  • the polymer composite film prepared in the step 2) is laid between the veneers, and the plywood bundle is first placed on a hot press to be heated and pressurized, and then moved to a cold press for pressurization and cooling;
  • the hot pressing temperature is 160 ° C
  • the hot pressing pressure is 0.8 MPa
  • the hot pressing time is 400 s
  • the cold pressing pressure is 0.9 MPa
  • the cold pressing time is 600 s.
  • step 2) The material mixed in the step 1) is added to an extrusion blown film machine or a casting machine to form a film, and a polymer composite film is obtained; wherein the screw temperatures are: 180 ° C, 175 ° C, 165 ° C, respectively. , 160 ° C, 150 ° C;
  • the polymer composite film prepared in the step 2) is laid between the veneers, and the plywood bundle is first placed on a hot press to be heated and pressurized, and then moved to a cold press for pressurization and cooling;
  • the hot pressing temperature is 155 ° C
  • the hot pressing pressure is 0.85 MPa
  • the hot pressing time is 350 s
  • the cold pressing pressure is 0.95 MPa
  • the cold pressing time is 600 s.
  • step 2) The material mixed in the step 1) is added to a casting machine to form a film, and a polymer composite film is obtained; wherein the screw temperatures are: 185 ° C, 175 ° C, 170 ° C, 160 ° C, 145 ° C, respectively. ;
  • the polymer composite film prepared in the step 2) is laid between the veneers, and the plywood bundle is first placed on a hot press to be heated and pressurized, and then moved to a cold press for pressurization and cooling;
  • the hot pressing temperature is 165 ° C
  • the hot pressing pressure is 0.95 MPa
  • the hot pressing time is 400 s
  • the cold pressing pressure is 1.05 MPa
  • the cold pressing time is 500 s.
  • novel aldehyde-free adhesive and plywood provided by the invention are suitable for the field of home decoration, building board and the like, which have requirements on the performance and environmental protection of the board.

Abstract

Disclosed in the present invention are a formaldehyde-free adhesive and a method for preparing same. The formaldehyde-free adhesive is a polymer composite film, and consists of 100 parts of resin and 15-25 parts of graft. The resin is one or more of high density polyethylene, low density polyethylene, an ethylene-octene copolymer, and an ethylene-vinyl acetate copolymer. The graft is one or more of grafts comprising grafting acrylic acid onto high density polyethylene, grafting acrylic acid onto low density polyethylene, grafting acrylic acid onto an ethylene-vinyl acetate copolymer, grafting acrylic acid onto linear low density polyethylene, and grafting acrylic acid onto an ethylene-octene copolymer. By applying the formaldehyde-free adhesive to plywood manufacturing, a novel formaldehyde-free plywood having a good mechanical property and no formaldehyde release can be made, thereby achieving widespread social benefits.

Description

一种无醛胶粘剂及其制备方法Aldehyde-free adhesive and preparation method thereof 技术领域Technical field
本发明属于胶粘剂的制备领域，具体涉及一种无醛胶粘剂及其制备方法。The invention belongs to the field of preparation of adhesives, in particular to an aldehyde-free adhesive and a preparation method thereof.
背景技术Background technique
热塑性树脂胶合板作为一种人造板工艺制备的木塑复合材料，以热塑性树脂胶膜作为粘接材料，生产便利清洁，杜绝甲醛污染，是一种极具前景的无醛级胶合板产品，特别适宜传统胶合板企业产品更新升级。但由于木材是一种不均匀的各向异性材料，由含有大量的极性羟基和酚羟基官能团的纤维素、半纤维素、木素以及抽提物等组成，表现出较强的化学极性和亲水性，当它与非极性热塑性树脂，如HDPE薄膜等胶合时，界面黏结力较弱，耐沸水能力差，极大了限制了该类材料的应用范围。As a wood-plastic composite material prepared by a wood-based panel process, the thermoplastic resin plywood is made of a thermoplastic resin film as a bonding material, which is convenient for cleaning and eliminates formaldehyde pollution. It is a promising aldehyde-free plywood product, which is particularly suitable for traditional Plywood enterprise product update and upgrade. However, since wood is a non-uniform anisotropic material, it is composed of cellulose, hemicellulose, lignin, and extracts containing a large amount of polar hydroxyl groups and phenolic hydroxyl functional groups, and exhibits strong chemical polarity. And hydrophilicity, when it is glued with non-polar thermoplastic resin, such as HDPE film, the interface bonding force is weak, and the boiling water resistance is poor, which greatly limits the application range of the material.
目前利用各种物化手段对木制原料进行处理，以提高木质材料与非极性热塑性树脂的相容性与结合能力的研究很多，如高温预处理以及偶联剂浸泡等。但由于预处理木制原料的成本较高，且预处理花费大量时间等问题制约了这些手段的发展。At present, there are many studies on the treatment of wood raw materials by various physical and chemical means to improve the compatibility and binding ability of wood materials and non-polar thermoplastic resins, such as high temperature pretreatment and coupling agent soaking. However, due to the high cost of pretreatment of wooden raw materials, and the pretreatment takes a lot of time and other issues, the development of these means is restricted.
制备聚合物复合材料薄膜，以提高其作为粘结剂时与木质原料的相容性和结合力，是提高热塑性树脂胶合板界面相容性和强度的较为简单有效的方法。将聚合物复合材料薄膜铺于单板之间，胶合板组坯先放在热压机上加热、加压，然后再移到冷压机上加压、冷却。得到一种新型无醛胶合板，具有力学性能好，无甲醛释放等特点，具有广泛的社会效益。The preparation of the polymer composite film to improve the compatibility and bonding force with the wood raw material as a binder is a relatively simple and effective method for improving the interfacial compatibility and strength of the thermoplastic resin plywood. The polymer composite film is placed between the veneers, and the plywood bundles are first placed on a hot press for heating and pressurization, and then moved to a cold press for pressurization and cooling. A novel aldehyde-free plywood is obtained, which has the characteristics of good mechanical properties, no formaldehyde release, and has wide social benefits.
发明内容Summary of the invention
本发明的目的在于针对目前传统胶合板产品的不足之处，提供一种新型无醛胶粘剂及其制备方法。采用该无醛胶粘剂制备胶合板，可提高胶粘剂与木质原料的相容性和结合力，且无甲醛释放，力学性能好，具有广泛的社会效益。The object of the present invention is to provide a novel aldehyde-free adhesive and a preparation method thereof for the deficiencies of the conventional plywood products. The use of the aldehyde-free adhesive to prepare plywood can improve the compatibility and bonding force of the adhesive and the wood raw material, and has no formaldehyde release, good mechanical properties and wide social benefits.
为实现上述目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种无醛胶粘剂，所述的无醛胶粘剂为聚合物复合材料薄膜；其原料组成按重量份数计为：树脂100份，接枝物15～25份；所述的接枝物为高密度聚乙烯接枝丙烯酸(接枝率15.9％)、低密度聚乙烯接枝丙烯酸(接枝率8.5％)、乙烯-醋酸乙烯共聚物接枝丙烯酸(接枝率11.1％)、线性低密度聚乙烯接枝丙烯酸(接枝率2.7％)、乙烯-辛烯共聚物接枝丙烯酸(接枝率5.4％)(以上均为自制)，高密度聚乙烯接枝马来酸酐、低密度聚乙烯接枝马来酸酐、线性低密度聚乙烯接枝马来酸酐(以上购自南京聚星高分子有限公司)，乙烯-辛烯共聚物接枝马来酸酐、乙烯-醋酸乙烯共聚物接枝马来酸酐(以上均购自吴江斯瑞达塑业有限公司)，高密度聚乙烯 接枝甲基丙烯酸缩水甘油酯、低密度聚乙烯接枝甲基丙烯酸缩水甘油酯、乙烯-醋酸乙烯共聚物接枝甲基丙烯酸缩水甘油酯、线性低密度聚乙烯接枝甲基丙烯酸缩水甘油酯、乙烯-辛烯共聚物接枝甲基丙烯酸缩水甘油酯(以上均购自扬州市恒辉化工有限公司)，高密度聚乙烯接枝丙烯酸甲酯/高密度聚乙烯接枝丙烯酸丁酯(质量比1:1)、低密度聚乙烯接枝丙烯酸甲酯/低密度聚乙烯接枝丙烯酸丁酯(质量比1:1)、乙烯-辛烯共聚物接枝丙烯酸甲酯/乙烯-辛烯共聚物接枝丙烯酸丁酯(质量比1:1)、线性低密度聚乙烯接枝丙烯酸甲酯/线性低密度聚乙烯接枝丙烯酸丁酯(质量比1:1)、乙烯-醋酸乙烯共聚物接枝丙烯酸甲酯/乙烯-醋酸乙烯共聚物丙烯酸丁酯(质量比1:1)，高密度聚乙烯接枝甲基丙烯酸甲酯(接枝率10.1％)、低密度聚乙烯接枝甲基丙烯酸甲酯(接枝率12.8％)、乙烯-辛烯共聚物接枝甲基丙烯酸甲酯(接枝率21.5％)、线性低密度聚乙烯接枝甲基丙烯酸甲酯(接枝率18.1％)、乙烯-醋酸乙烯共聚物接枝甲基丙烯酸甲酯(接枝率7.2％)的一种或两种(以上均为自制)。An aldehyde-free adhesive, wherein the aldehyde-free adhesive is a polymer composite film; the raw material composition is: by weight: 100 parts of the resin, 15-25 parts of the graft; the graft is high density Polyethylene grafted acrylic acid (grafting rate 15.9%), low density polyethylene grafted acrylic acid (grafting rate 8.5%), ethylene-vinyl acetate copolymer grafted acrylic acid (grafting rate 11.1%), linear low density polyethylene Grafted acrylic acid (grafting rate 2.7%), ethylene-octene copolymer grafted acrylic acid (grafting rate 5.4%) (all of which are self-made), high density polyethylene grafted maleic anhydride, low density polyethylene grafted Maleic anhydride, linear low density polyethylene grafted maleic anhydride (supplied from Nanjing Juxing Polymer Co., Ltd.), ethylene-octene copolymer grafted maleic anhydride, ethylene-vinyl acetate copolymer grafted maleic anhydride (The above are all purchased from Wujiang Sruida Plastic Industry Co., Ltd.), high density polyethylene Grafted glycidyl methacrylate, low density polyethylene grafted glycidyl methacrylate, ethylene-vinyl acetate copolymer grafted glycidyl methacrylate, linear low density polyethylene grafted glycidyl methacrylate , ethylene-octene copolymer grafted glycidyl methacrylate (all purchased from Yangzhou Henghui Chemical Co., Ltd.), high density polyethylene grafted methyl acrylate / high density polyethylene grafted butyl acrylate (quality Ratio 1:1), low density polyethylene grafted methyl acrylate/low density polyethylene grafted butyl acrylate (mass ratio 1:1), ethylene-octene copolymer grafted methyl acrylate/ethylene-octene copolymer Grafted butyl acrylate (mass ratio 1:1), linear low density polyethylene grafted methyl acrylate / linear low density polyethylene grafted butyl acrylate (mass ratio 1:1), ethylene-vinyl acetate copolymer Methyl acrylate/ethylene-vinyl acetate copolymer butyl acrylate (mass ratio 1:1), high density polyethylene grafted methyl methacrylate (grafting rate 10.1%), low density polyethylene grafted methacrylic acid Methyl ester (grafting rate 12.8%), ethylene-octene Grafted with methyl methacrylate (graft ratio: 21.5%), linear low-density polyethylene grafted with methyl methacrylate (graft ratio: 18.1%), ethylene-vinyl acetate copolymer grafted with methyl methacrylate ( One or two of the graft ratios of 7.2%) (all of which are self-made).
无醛胶粘剂的制备方法为：将树脂和接枝物充分混合并置于鼓风干燥箱中，40～60℃干燥5～7h，将混合好的物料加入到挤出吹膜机或流延机中进行成膜，得到聚合物复合材料薄膜。The aldehyde-free adhesive is prepared by thoroughly mixing the resin and the graft in a blast drying oven, drying at 40 to 60 ° C for 5 to 7 hours, and adding the mixed material to the extrusion blown film machine or the casting machine. Film formation was carried out to obtain a polymer composite film.
混合物料加入到挤出吹膜机或流延机中进行成膜时，其螺杆温度分别为：模头175～185℃、三通段170～180℃、第三段160～170℃、第二段155～165℃、入料段145～155℃。When the mixture is added to an extrusion blown film machine or a casting machine to form a film, the screw temperatures are: 175 to 185 ° C for the die, 170 to 180 ° C for the three-way segment, and 160 to 170 ° C for the third segment, and the second. Section 155 ~ 165 ° C, feed section 145 ~ 155 ° C.
将如上所述的无醛胶粘剂应用到胶合板中：将聚合物复合材料薄膜铺于单板之间，胶合板组坯先放在热压机上加热、加压，然后再移到冷压机上加压、冷却；热压机上的热压温度为140～170℃，热压压力为0.7～1.0MPa，热压时间为300～500s；冷压机上的冷压压力为0.7～1.1MPa，冷压时间为400s～600s。The aldehyde-free adhesive as described above is applied to the plywood: the polymer composite film is laid between the veneers, and the plywood bundle is first placed on a hot press to be heated and pressurized, and then moved to a cold press for pressurization. Cooling; the hot pressing temperature on the hot press is 140-170 ° C, the hot pressing pressure is 0.7-1.0 MPa, the hot pressing time is 300-500 s; the cold pressing pressure on the cold press is 0.7-1.1 MPa, cold pressing time It is 400s to 600s.
本发明的有益效果在于：The beneficial effects of the invention are:
(1)本发明所得的新型无醛胶粘剂用于制备胶合板时，可提高胶粘剂与木质原料的相容性和结合力，且无甲醛释放，力学性能好，生产便利清洁，其胶合板符合国家标准GB/T17657-2013《人造板及饰面人造板理化性能实验方法》一类胶合板胶合强度的标准，且无甲醛释放，强度达到一类板标准；(1) The novel aldehyde-free adhesive obtained by the invention can improve the compatibility and bonding force of the adhesive and the wood raw material when preparing the plywood, and has no formaldehyde release, good mechanical property, convenient production and cleaning, and the plywood meets the national standard GB. /T17657-2013 "Experimental Methods for Physical and Chemical Properties of Artificial Panels and Finished Panels" A standard for the bonding strength of a class of plywood, and no formaldehyde release, the strength reaches a class of board standards;
(2)本发明所得的新型无醛胶粘剂及胶合板，安全环保，适应当今市场的需求，制备方法科学合理、工序简单、操作性强，改善了目前传统胶合板产品的不足之处，并扩展了其的应用范围，具有广泛的市场前景和显著的社会效益。(2) The novel aldehyde-free adhesive and plywood obtained by the invention are safe and environmentally friendly, and are suitable for the needs of the current market. The preparation method is scientific and reasonable, the process is simple, and the operability is strong, and the defects of the conventional plywood products are improved and expanded. The scope of application has broad market prospects and significant social benefits.
具体实施方式detailed description
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。 In order to make the content of the present invention more understandable, the technical solutions described in the present invention are further described below in conjunction with specific embodiments, but the present invention is not limited thereto.
实施例1Example 1
1)由以下重量份数的原料制成：高密度聚乙烯20份、低密度聚乙烯80份、高密度聚乙烯接枝丙烯酸10份、乙烯-醋酸乙烯共聚物接枝甲基丙烯酸缩水甘油酯15份，充分混合并置于鼓风干燥箱中50℃干燥6h；1) Made of the following parts by weight of raw materials: 20 parts of high density polyethylene, 80 parts of low density polyethylene, 10 parts of high density polyethylene grafted acrylic acid, ethylene-vinyl acetate copolymer grafted glycidyl methacrylate 15 parts, thoroughly mixed and placed in a blast drying oven at 50 ° C for 6 h;
2)将所述步骤1)中混合好的物料加入到挤出吹膜机中进行成膜，得到聚合物复合材料薄膜；其中螺杆温度分别为：185℃、180℃、165℃、155℃、145℃；2) The material mixed in the step 1) is added to an extrusion blown film machine to form a film, and a polymer composite film is obtained; wherein the screw temperatures are: 185 ° C, 180 ° C, 165 ° C, 155 ° C, 145 ° C;
3)将所述步骤2)制备的聚合物复合材料薄膜铺于单板之间，胶合板组坯先放在热压机上加热、加压，然后再移到冷压机上加压、冷却；其中热压温度为150℃，热压压力为0.7MPa，热压时间为400s，冷压压力为0.8MPa，冷压时间为500s。3) The polymer composite film prepared in the step 2) is laid between the veneers, and the plywood bundle is first placed on a hot press to be heated and pressurized, and then moved to a cold press for pressurization and cooling; The hot pressing temperature is 150 ° C, the hot pressing pressure is 0.7 MPa, the hot pressing time is 400 s, the cold pressing pressure is 0.8 MPa, and the cold pressing time is 500 s.
实施例2Example 2
1)由以下重量份数的原料制成：高密度聚乙烯80份、低密度聚乙烯20份，高密度聚乙烯接枝丙烯酸15份，充分混合并置于鼓风干燥箱中50℃干燥6h；1) Made of the following parts by weight of raw materials: 80 parts of high-density polyethylene, 20 parts of low-density polyethylene, 15 parts of high-density polyethylene grafted acrylic acid, thoroughly mixed and placed in a blast drying oven at 50 ° C for 6 h. ;
2)将所述步骤1)中混合好的物料加入到流延机中进行成膜，得到聚合物复合材料薄膜；其中螺杆温度分别为：180℃、175℃、165℃、160℃、150℃；2) The material mixed in the step 1) is added to a casting machine to form a film, and a polymer composite film is obtained; wherein the screw temperatures are: 180 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C, respectively. ;
3)将所述步骤2)制备的聚合物复合材料薄膜铺于单板之间，胶合板组坯先放在热压机上加热、加压，然后再移到冷压机上加压、冷却；其中热压温度为160℃，热压压力为0.8MPa，热压时间为400s，冷压压力为0.9MPa，冷压时间为600s。3) The polymer composite film prepared in the step 2) is laid between the veneers, and the plywood bundle is first placed on a hot press to be heated and pressurized, and then moved to a cold press for pressurization and cooling; The hot pressing temperature is 160 ° C, the hot pressing pressure is 0.8 MPa, the hot pressing time is 400 s, the cold pressing pressure is 0.9 MPa, and the cold pressing time is 600 s.
实施例3Example 3
1)由以下重量份数的原料制成：低密度聚乙烯30份、乙烯-辛烯共聚物30份、线性低密度聚乙烯40份，低密度聚乙烯接枝丙烯酸甲酯/丙烯酸丁酯(50/50)25份，充分混合并置于鼓风干燥箱中50℃干燥6h；1) Made of the following parts by weight of raw materials: 30 parts of low density polyethylene, 30 parts of ethylene-octene copolymer, 40 parts of linear low density polyethylene, low density polyethylene grafted methyl acrylate / butyl acrylate ( 50/50) 25 parts, fully mixed and placed in a blast drying oven at 50 ° C for 6 h;
2)将所述步骤1)中混合好的物料加入到挤出吹膜机或流延机中进行成膜，得到聚合物复合材料薄膜；其中螺杆温度分别为：180℃、175℃、165℃、160℃、150℃；2) The material mixed in the step 1) is added to an extrusion blown film machine or a casting machine to form a film, and a polymer composite film is obtained; wherein the screw temperatures are: 180 ° C, 175 ° C, 165 ° C, respectively. , 160 ° C, 150 ° C;
3)将所述步骤2)制备的聚合物复合材料薄膜铺于单板之间，胶合板组坯先放在热压机上加热、加压，然后再移到冷压机上加压、冷却；其中热压温度为155℃，热压压力为0.85MPa，热压时间为350s，冷压压力为0.95MPa，冷压时间为600s。3) The polymer composite film prepared in the step 2) is laid between the veneers, and the plywood bundle is first placed on a hot press to be heated and pressurized, and then moved to a cold press for pressurization and cooling; The hot pressing temperature is 155 ° C, the hot pressing pressure is 0.85 MPa, the hot pressing time is 350 s, the cold pressing pressure is 0.95 MPa, and the cold pressing time is 600 s.
实施例4Example 4
1)由以下重量份数的原料制成：低密度聚乙烯50份、乙烯-辛烯共聚物50份、高密度聚乙烯接枝马来酸酐10份、低密度聚乙烯接枝甲基丙烯酸甲酯15份，充分混合并置于鼓风干燥箱中50℃干燥6h； 1) Made of the following parts by weight of raw materials: 50 parts of low density polyethylene, 50 parts of ethylene-octene copolymer, 10 parts of high density polyethylene grafted maleic anhydride, low density polyethylene grafted methacrylic acid 15 parts of ester, fully mixed and placed in a forced air oven at 50 ° C for 6h;
2)将所述步骤1)中混合好的物料加入到流延机中进行成膜，得到聚合物复合材料薄膜；其中螺杆温度分别为：185℃、175℃、170℃、160℃、145℃；2) The material mixed in the step 1) is added to a casting machine to form a film, and a polymer composite film is obtained; wherein the screw temperatures are: 185 ° C, 175 ° C, 170 ° C, 160 ° C, 145 ° C, respectively. ;
3)将所述步骤2)制备的聚合物复合材料薄膜铺于单板之间，胶合板组坯先放在热压机上加热、加压，然后再移到冷压机上加压、冷却；其中热压温度为165℃，热压压力为0.95MPa，热压时间为400s，冷压压力为1.05MPa，冷压时间为500s。3) The polymer composite film prepared in the step 2) is laid between the veneers, and the plywood bundle is first placed on a hot press to be heated and pressurized, and then moved to a cold press for pressurization and cooling; The hot pressing temperature is 165 ° C, the hot pressing pressure is 0.95 MPa, the hot pressing time is 400 s, the cold pressing pressure is 1.05 MPa, and the cold pressing time is 500 s.
本发明所提供的新型无醛胶粘剂及胶合板适用于家庭装修，建筑板材等对板材性能及环保有要求的领域。The novel aldehyde-free adhesive and plywood provided by the invention are suitable for the field of home decoration, building board and the like, which have requirements on the performance and environmental protection of the board.
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。 The above are only the preferred embodiments of the present invention, and all changes and modifications made to the scope of the present invention should fall within the scope of the present invention.

Claims (4)

  1. 一种无醛胶粘剂，其特征在于：所述的无醛胶粘剂为聚合物复合材料薄膜；其原料组成按重量份计为：树脂100份，接枝物15～25份；所述的树脂为高密度聚乙烯、低密度聚乙烯、乙烯-辛烯共聚物、乙烯-醋酸乙烯共聚物中的一种或多种；所述的接枝物为高密度聚乙烯接枝丙烯酸、低密度聚乙烯接枝丙烯酸、乙烯-醋酸乙烯共聚物接枝丙烯酸、线性低密度聚乙烯接枝丙烯酸、乙烯-辛烯共聚物接枝丙烯酸、高密度聚乙烯接枝马来酸酐、低密度聚乙烯接枝马来酸酐、线性低密度聚乙烯接枝马来酸酐、乙烯-辛烯共聚物接枝马来酸酐、乙烯-醋酸乙烯共聚物接枝马来酸酐、高密度聚乙烯接枝甲基丙烯酸缩水甘油酯、低密度聚乙烯接枝甲基丙烯酸缩水甘油酯、乙烯-醋酸乙烯共聚物接枝甲基丙烯酸缩水甘油酯、线性低密度聚乙烯接枝甲基丙烯酸缩水甘油酯、乙烯-辛烯共聚物接枝甲基丙烯酸缩水甘油酯、高密度聚乙烯接枝丙烯酸甲酯/丙烯酸丁酯、低密度聚乙烯接枝丙烯酸甲酯/丙烯酸丁酯、乙烯-辛烯共聚物接枝丙烯酸甲酯/丙烯酸丁酯、线性低密度聚乙烯接枝丙烯酸甲酯/丙烯酸丁酯、乙烯-醋酸乙烯共聚物接枝丙烯酸甲酯/丙烯酸丁酯、高密度聚乙烯接枝甲基丙烯酸甲酯、低密度聚乙烯接枝甲基丙烯酸甲酯、乙烯-辛烯共聚物接枝甲基丙烯酸甲酯、线性低密度聚乙烯接枝甲基丙烯酸甲酯、乙烯-醋酸乙烯共聚物接枝甲基丙烯酸甲酯的一种或两种。An aldehyde-free adhesive, characterized in that: the aldehyde-free adhesive is a polymer composite film; the raw material composition is: by weight: 100 parts of a resin, 15 to 25 parts of a graft; the resin is high One or more of density polyethylene, low density polyethylene, ethylene-octene copolymer, ethylene-vinyl acetate copolymer; the graft is high density polyethylene grafted acrylic, low density polyethylene Acrylic acid, ethylene-vinyl acetate copolymer grafted acrylic acid, linear low density polyethylene grafted acrylic acid, ethylene-octene copolymer grafted acrylic acid, high density polyethylene grafted maleic anhydride, low density polyethylene grafted Malay Anhydride, linear low density polyethylene grafted maleic anhydride, ethylene-octene copolymer grafted maleic anhydride, ethylene-vinyl acetate copolymer grafted maleic anhydride, high density polyethylene grafted glycidyl methacrylate, Low density polyethylene grafted glycidyl methacrylate, ethylene-vinyl acetate copolymer grafted glycidyl methacrylate, linear low density polyethylene grafted glycidyl methacrylate, ethylene-xin Copolymer grafted glycidyl methacrylate, high density polyethylene grafted methyl acrylate / butyl acrylate, low density polyethylene grafted methyl acrylate / butyl acrylate, ethylene - octene copolymer grafted methyl acrylate /butyl acrylate, linear low density polyethylene grafted methyl acrylate / butyl acrylate, ethylene - vinyl acetate copolymer grafted methyl acrylate / butyl acrylate, high density polyethylene grafted methyl methacrylate, low density Polyethylene grafted methyl methacrylate, ethylene-octene copolymer grafted methyl methacrylate, linear low density polyethylene grafted methyl methacrylate, ethylene-vinyl acetate copolymer grafted methyl methacrylate One or two.
  2. 一种制备如权利要求1所述的无醛胶粘剂的方法，其特征在于：树脂和接枝物充分混合并置于鼓风干燥箱中，40～60℃干燥5～7h，将混合好的物料加入到挤出吹膜机或流延机中进行成膜，得到聚合物复合材料薄膜。A method for preparing an aldehyde-free adhesive according to claim 1, wherein the resin and the graft are thoroughly mixed and placed in a blast drying oven, dried at 40 to 60 ° C for 5 to 7 hours, and the mixed materials are mixed. Film formation is carried out by adding to an extrusion blown film machine or a casting machine to obtain a polymer composite material film.
  3. 根据权利要求2所述的无醛胶粘剂的制备方法，其特征在于：加入到挤出吹膜机或流延机中进行成膜，其螺杆温度分别为：模头175～185℃、三通段170～180℃、第三段160～170℃、第二段155～165℃、入料段145～155℃。The method for preparing an aldehyde-free adhesive according to claim 2, wherein the film is formed by adding to an extrusion blown film machine or a casting machine, and the screw temperatures are respectively: a die of 175 to 185 ° C and a three-way section. 170-180 ° C, the third section 160 ~ 170 ° C, the second section 155 ~ 165 ° C, the feed section 145 ~ 155 ° C.
  4. 一种如权利要求1所述的无醛胶粘剂在胶合板中的应用，其特征在于：将聚合物复合材料薄膜铺于单板之间，胶合板组坯先放在热压机上加热、加压，然后再移到冷压机上加压、冷却；热压机上的热压温度为140～170℃，热压压力为0.7～1.0MPa，热压时间为300～500s；冷压机上的冷压压力为0.7～1.1MPa，冷压时间为400～600s。 The use of the aldehyde-free adhesive according to claim 1 in a plywood, characterized in that a polymer composite film is laid between the veneers, and the plywood bundling is first placed on a hot press to heat and pressurize, and then Then move to the cold press to pressurize and cool; the hot pressing temperature on the hot press is 140-170 ° C, the hot pressing pressure is 0.7-1.0 MPa, the hot pressing time is 300-500 s; the cold pressing pressure on the cold press It is 0.7 to 1.1 MPa, and the cold pressing time is 400 to 600 s.
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CN104356977A (en) * 2014-11-27 2015-02-18 河源市普立隆新材料科技有限公司 Preparation method of adhesive resin for multilayer coextruded plastic composite hose
CN104449469A (en) * 2014-11-28 2015-03-25 河源市普立隆新材料科技有限公司 Method for preparing polyethylene type adhesive resin for multilayer co-extrusion barrier package
CN104531005A (en) * 2014-12-19 2015-04-22 上海邦中新材料有限公司 Bonding resin for steel strip reinforced polyethylene pipe for underground drainage
CN105505257A (en) * 2016-01-06 2016-04-20 福州大学 Non-formaldehyde adhesive and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
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CN109679578A (en) * 2018-12-06 2019-04-26 书香门地（上海）美学家居股份有限公司 A kind of toughness dregs of beans albumen adhesive and preparation method thereof
CN109679578B (en) * 2018-12-06 2022-09-06 书香门地集团股份有限公司 Tough soybean meal protein adhesive and preparation method thereof
CN113150719A (en) * 2021-04-28 2021-07-23 刘杨 Zero-formaldehyde adhesive, preparation method and application
CN114231211A (en) * 2021-12-30 2022-03-25 上海邦中高分子材料股份有限公司 Special adhesive resin for plastic-lined composite pipe by taking liquid medicine soaking as pretreatment mode of steel pipe and preparation method thereof
CN115260914A (en) * 2022-06-28 2022-11-01 山东大学威海工业技术研究院 Aldehyde-free adhesive and preparation method thereof

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