CN102234493B - Plant composite adhesive for man-made board and preparation method thereof - Google Patents

Plant composite adhesive for man-made board and preparation method thereof Download PDF

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Publication number
CN102234493B
CN102234493B CN201010152531A CN201010152531A CN102234493B CN 102234493 B CN102234493 B CN 102234493B CN 201010152531 A CN201010152531 A CN 201010152531A CN 201010152531 A CN201010152531 A CN 201010152531A CN 102234493 B CN102234493 B CN 102234493B
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China
Prior art keywords
starch glue
tackiness agent
water
vinyl acetate
artificial board
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CN201010152531A
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Chinese (zh)
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CN102234493A (en
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王钱生
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王钱生
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Abstract

The invention discloses a plant composite adhesive for a man-made board and a preparation method thereof. The adhesive comprises a main agent, wherein the main agent is prepared from the following raw materials in part by weight: 30 to 45 parts of denaturated starch glue, 1 to 3 parts of methylcellulose, 3 to 5 parts of polyvinyl alcohol, 0.5 to 1 part of urea, 30 to 45 parts of vinyl acetate-ethylene copolymer emulsion, 4 to 6 parts of bentonite, 0.4 to 0.8 part of sodium hexametaphosphate, 15 to 25 parts of water, 0.08 to 0.2 part of defoaming agent and 0.08 to 0.2 part of preservative, wherein the denaturated starch glue is emulsion with the solid content of 15 to 20 percent, which is prepared by adding pre-gelatinized cassava starch into water with the temperature of between 30 and 45DEG C. Compared with the prior art, by crosslinking, plasticizing and further polymerizing the vinyl acetate-ethylene copolymer emulsion, the plant composite adhesive has the advantages that: hydrophilic groups in the denaturated starch glue are obviously improved, the adhesive strength and water resistance are greatly improved, the raw materials are simple and readily available, the production cost is low, and the storage period is longer than 12 months.

Description

One kind of plant combined artificial board material tackiness agent and preparation method thereof
Technical field
The present invention relates to a kind of tackiness agent, be specifically related to kind of plant combined artificial board material tackiness agent and preparation method thereof.
Background technology
The forest resourceies of China are deficient, and in order to remedy the deficiency of timber resources, the wood-based plate industry development is rapid, therefore driven the flourish of wood adhesive industry.According to statistics, total consumption of the wood adhesive of China in 2007 is more than 300 ten thousand tons, and is ascendant trend year by year.Existing wood adhesive kind is a lot; But main use urea-formaldehyde resin adhesive and Phenol aldehyde resin on producing are because the main raw material of this type glue is a formaldehyde, therefore; In the significant period of time of production and use, can discharge free formaldehyde continuously, it is healthy to influence environment and user.Plant amylum class tackiness agent can extensively not accepted by the human consumer owing to not containing formaldehyde.Like publication number is the Chinese invention patent of CN101508876; A kind of modified starch based adhesion agent for lumber and preparation method are disclosed; This tackiness agent is to be main raw material with starch and Z 150PH; Make tackiness agent host through starch being carried out carry out grafting with Z 150PH after the pre-treatment such as gelatinization and oxidation, carry out modification to wherein adding aqueous SBS emulsion or melamine formaldehyde resin again, made the lower tackiness agent of free formaldehyde content.With the artificial board that this glue is produced, free formaldehyde release reaches the E0 grade standard, but the large usage quantity of the Z 150PH of this tackiness agent, cost is higher relatively, is difficult to utilization and extention.
Summary of the invention
It is lower that the technical problem that the present invention will solve provides a kind of production cost, and main performance index such as adhesive strength, water tolerance all reach plant combined artificial board material tackiness agent of GB GB/T5849-2006 requirement and preparation method thereof.Artificial board burst size of methanal≤0.2mg/L with tackiness agent of the present invention is produced does not contain objectionable impuritiess such as benzene,toluene,xylene, phenols.
The technical scheme that the present invention adopts is following:
One kind of plant combined artificial board material tackiness agent comprises host, and said host is processed by the raw material of following weight parts:
Modified starch glue 30~45, methylcellulose gum 1~3, Z 150PH 3~5, urea 0.5~1, vinyl acetate-ethylene copolymerization emulsions 30~45, bentonite 4~6, Sodium hexametaphosphate 99 0.4~0.8, water 15~25, skimmer 0.08~0.2, sanitas 0.08~0.2;
Described modified starch glue is to be 15~25% emulsion by the solid content that preparatory gelatinization tapioca(flour) under agitation joins furnishing in 30 ℃~45 ℃ water.
Above-mentioned plant combined artificial board material tackiness agent can be applicable to the finger plate, the production of cold pressing glue plywood, artificial jigsaw and other artificial boards; When being used for the more coarse mechanism plate of splicing face, preferably also comprise solidifying agent, said solidifying agent is a diphenylmethanediisocyanate, and when specifically using, the weight ratio of host and solidifying agent is 100: 5~15.
In the above-mentioned prescription,
Described preparatory gelatinization tapioca(flour) is the commercially available prod, also can prepare voluntarily by ordinary method.
Described skimmer is propyl carbinol or tributyl phosphate, and sanitas is RH-893 or Sodium Benzoate.
The ethylene content of described vinyl acetate-ethylene copolymerization emulsions is 14~18% (quality).
The preparation method of the above plant combined artificial board material tackiness agent, its step is following:
1) get preparatory gelatinization tapioca(flour) and join under agitation that to process solid content in 30 ℃~45 ℃ water be 15~25% modified starch glue, subsequent use;
2) get Z 150PH and place water, be warming up to 90~95 ℃, add skimmer, Z 150PH is dissolved fully, be cooled to 45~75 ℃ subsequent use;
3) press proportional quantity, add methylcellulose gum when getting modified starch glue and being heated to 65~75 ℃, stir, add the polyvinyl alcohol water solution and the urea that are cooled to 45~75 ℃, reacted 20~40 minutes, obtain graft starch glue; Described reinforced and reaction is all under agitation carried out;
4) gained graft starch glue is cooled to 30~55 ℃, under agitation adds vinyl acetate-ethylene copolymerization emulsions, and insulation reaction 20~40 minutes adds bentonite, Sodium hexametaphosphate 99 and sanitas after being cooled to normal temperature, and the after-filtration discharging that stirs promptly gets product.
Step 2) in, said skimmer is propyl carbinol or tributyl phosphate, and sanitas is RH-893 or Sodium Benzoate.
In the step 4), the ethylene content of said vinyl acetate-ethylene copolymerization emulsions is 14~18% (quality).
Compared with prior art; The invention has the advantages that: through with crosslinked, the plasticising and the further polymerization of high molecular polymer vinyl acetate-ethylene; Make in the modified starch glue hydrophilic radical be improved significantly; Form complete multidimensional network structure, improved the force of cohesion of glue greatly, thereby improved adhesive strength and water tolerance; In addition, in glue, add bentonite, reduced the time that moisture content gets into wood fibre fast, it is too fast to prevent that monolithic from crossing the glue after drying, thereby prolonged the engineering time; Moreover, produce and use in pollution-free, no Carbon emission, meet national environmental protection and low-carbon economy policy, raw material is simple and easy to, production cost is low, uses more extensively, can reach more than 12 months storage period.
Embodiment
With embodiment the present invention is described further below, but the present invention is not limited to these embodiment.
Embodiment 1
Adhesive formulation:
Solid content is 18% modified starch glue 30Kg, methylcellulose gum 3Kg, Z 150PH 3Kg, urea 0.5Kg, vinyl acetate-ethylene copolymerization emulsions 45Kg, bentonite 6Kg, Sodium hexametaphosphate 99 0.8Kg, water 15Kg, propyl carbinol 0.08Kg, RH-893 0.08Kg.
The preparation method:
1) get preparatory gelatinization tapioca(flour) and add under agitation that to process solid content in 30 ℃ of water be 18% modified starch glue, it is subsequent use to take out 30Kg;
2) get Z 150PH and place water, be warming up to 95 ℃, make Z 150PH dissolve (in the dissolution process add 0.08Kg propyl carbinol) fully, be cooled to 45 ℃ subsequent use;
Add methylcellulose gum when 3) above-mentioned 30Kg modified starch glue being heated to 70 ℃, stir, add the polyvinyl alcohol water solution and the urea that are cooled to 45 ℃, insulation reaction 40 minutes obtains graft starch glue; Described reinforced and reaction is all under agitation carried out;
4) gained graft starch glue naturally cools to 30 ℃, under agitation adds vinyl acetate-ethylene copolymerization emulsions, and insulation reaction 40 minutes adds bentonite, Sodium hexametaphosphate 99 and RH-893 after being cooled to normal temperature, and the after-filtration discharging that stirs promptly gets product.
Embodiment 2
Adhesive formulation:
Solid content is 21% modified starch glue 38Kg, methylcellulose gum 2Kg, Z 150PH 4Kg, urea 0.75Kg, vinyl acetate-ethylene copolymerization emulsions 38Kg, bentonite 5Kg, Sodium hexametaphosphate 99 0.6Kg, water 20Kg, propyl carbinol 0.15Kg, RH-893 0.15Kg.
The preparation method:
1) get preparatory gelatinization tapioca(flour) and add under agitation that to process solid content in 40 ℃ of water be 21% modified starch glue, it is subsequent use to take out 38Kg;
2) get Z 150PH and place water, be warming up to 90 ℃, make Z 150PH dissolve (in the dissolution process add 0.15Kg propyl carbinol) fully, be cooled to 65 ℃ subsequent use;
Add methylcellulose gum when 3) above-mentioned 38Kg modified starch glue being heated to 65 ℃, stir, add the polyvinyl alcohol water solution and the urea that are cooled to 65 ℃, insulation reaction 30 minutes obtains graft starch glue; Described reinforced and reaction is all under agitation carried out;
4) gained graft starch glue naturally cools to 55 ℃, under agitation adds vinyl acetate-ethylene copolymerization emulsions, reacts 30 minutes, adds bentonite, Sodium hexametaphosphate 99 and RH-893 after being cooled to normal temperature, and the after-filtration discharging that stirs promptly gets product.
The tackiness agent that uses this embodiment to make prepares core-board with ordinary method, detects by GB/T5849-2006 " core-board ", and detected result is as shown in table 1 below; Detect the objectionable impurities in the stick is arranged by GB18580-2001, its result is as shown in table 2 below:
Table 1:
Table 2:
Embodiment 3
Adhesive formulation:
Solid content is 25% modified starch glue 45Kg, methylcellulose gum 1Kg, Z 150PH 5Kg, urea 1Kg, vinyl acetate-ethylene copolymerization emulsions 30Kg, bentonite 4Kg, Sodium hexametaphosphate 99 0.4Kg, water 25Kg, tributyl phosphate 0.2Kg, Sodium Benzoate 0.2Kg.
The preparation method:
1) get preparatory gelatinization tapioca(flour) and add under agitation that to process solid content in 45 ℃ of water be 25% modified starch glue, it is subsequent use to take out 45Kg;
2) get Z 150PH and place water, be warming up to 93 ℃ and make Z 150PH dissolve (in the dissolution process add 0.2Kg tributyl phosphate) fully, be cooled to 75 ℃ subsequent use;
Add methylcellulose gum when 3) above-mentioned 45Kg modified starch glue being heated to 75 ℃, stir, add the polyvinyl alcohol water solution and the urea that are cooled to 75 ℃, insulation reaction 20 minutes obtains graft starch glue; Described reinforced and reaction is all under agitation carried out;
4) gained graft starch glue is cooled to 40 ℃, under agitation adds vinyl acetate-ethylene copolymerization emulsions, and insulation reaction 20 minutes adds bentonite, Sodium hexametaphosphate 99 and Sodium Benzoate after being cooled to normal temperature, and the after-filtration discharging that stirs promptly gets product.
Embodiment 4
Adhesive formulation:
Host: solid content is 15% modified starch glue 40Kg, methylcellulose gum 2Kg, Z 150PH 3Kg, urea 0.6Kg, vinyl acetate-ethylene copolymerization emulsions 35Kg, bentonite 5.5Kg, Sodium hexametaphosphate 99 0.7Kg, water 18Kg, tributyl phosphate 0.1Kg, Sodium Benzoate 0.1Kg.
Solidifying agent: diphenylmethanediisocyanate, 10.2Kg.
The preparation method:
1) get preparatory gelatinization tapioca(flour) and add under agitation that to process solid content in 35 ℃ of water be 15% modified starch glue, it is subsequent use to take out 40Kg;
2) get Z 150PH and place water, be warming up to 95 ℃, make Z 150PH dissolve (in the dissolution process add 0.1Kg tributyl phosphate) fully, be cooled to 60 ℃ subsequent use;
Add methylcellulose gum when 3) above-mentioned 40Kg modified starch glue being heated to 65 ℃, be cooled to 60 ℃ polyvinyl alcohol water solution and urea, insulation reaction 35 minutes obtains graft starch glue; Described reinforced and reaction is all under agitation carried out;
4) gained graft starch glue is cooled to 45 ℃, under agitation adds vinyl acetate-ethylene copolymerization emulsions, and insulation reaction 25 minutes adds bentonite, Sodium hexametaphosphate 99 and Sodium Benzoate after being cooled to normal temperature, and the after-filtration discharging that stirs promptly gets.
During concrete the application, host and solidifying agent are mixed the back use get final product.

Claims (6)

1. a kind of plant combined artificial board material tackiness agent comprises host, and it is characterized in that: said host is processed by the raw material of following weight parts:
Modified starch glue 30~45, methylcellulose gum 1~3, Z 150PH 3~5, urea 0.5~1, vinyl acetate-ethylene copolymerization emulsions 30~45, bentonite 4~6, Sodium hexametaphosphate 99 0.4~0.8, water 15~25, skimmer 0.08~0.2, sanitas 0.08~0.2;
Described modified starch glue is to be 15~25% emulsion by the solid content that preparatory gelatinization tapioca(flour) under agitation joins furnishing in 30 ℃~45 ℃ water;
Described plant combined artificial board material tackiness agent also comprises solidifying agent, and said solidifying agent is a diphenylmethanediisocyanate.
2. plant combined artificial board material tackiness agent according to claim 1 is characterized in that: said skimmer is propyl carbinol or tributyl phosphate, and sanitas is RH-893 or Sodium Benzoate.
3. plant combined artificial board material tackiness agent according to claim 1 and 2 is characterized in that: the content of ethene is 14~18% quality in the vinyl acetate-ethylene copolymerization emulsions.
4. the preparation method of the said plant combined artificial board material of claim 1 tackiness agent, the step that wherein prepares host is following:
1) gets a certain amount of preparatory gelatinization tapioca(flour) and join under agitation that to process solid content in 30 ℃~45 ℃ water be that 15~25% modified starch glue is subsequent use;
2) get Z 150PH and place water, be warming up to 90~95 ℃, add skimmer, Z 150PH is dissolved fully, be cooled to 45~75 ℃ subsequent use;
3) press proportional quantity, add methylcellulose gum when getting modified starch glue and being heated to 65~75 ℃, stir, add the polyvinyl alcohol water solution and the urea that are cooled to 45~75 ℃, reacted 20~40 minutes, obtain graft starch glue; Described reinforced and reaction is all under agitation carried out;
4) gained graft starch glue is cooled to 30~55 ℃, under agitation adds vinyl acetate-ethylene copolymerization emulsions, and insulation reaction 20~40 minutes adds bentonite, Sodium hexametaphosphate 99 and sanitas after being cooled to normal temperature, and the after-filtration discharging that stirs promptly gets host.
5. the preparation method of plant combined artificial board material tackiness agent according to claim 4 is characterized in that: said skimmer is propyl carbinol or tributyl phosphate, and sanitas is RH-893 or Sodium Benzoate.
6. the preparation method of plant combined artificial board material tackiness agent according to claim 4 is characterized in that: the ethylene content of vinyl acetate-ethylene copolymerization emulsions is 14~18% quality.
CN201010152531A 2010-04-21 2010-04-21 Plant composite adhesive for man-made board and preparation method thereof CN102234493B (en)

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CN102766422B (en) * 2012-05-16 2014-03-05 桐乡嘉力丰实业股份有限公司 Glutinous rice wet glue and preparation method thereof
CN102977810B (en) * 2012-10-30 2015-11-25 苏州市德莱尔建材科技有限公司 A kind of based Wood Adhesives and preparation method thereof
CN104845561A (en) * 2015-05-06 2015-08-19 赣州市金东门化工有限公司 Wood board jointing glue with superstrong adhesion force
CN104927756A (en) * 2015-05-29 2015-09-23 柳州市东汇木业有限公司 Production method of panel adhesive
CN106079014A (en) * 2016-06-27 2016-11-09 苏州市鼎立包装有限公司 A kind of stalk is for wooden packing material and preparation method thereof
CN106147649B (en) * 2016-06-28 2018-06-22 广东宝雅纸业有限公司 A kind of corrugated board low temperature adhesion glue and application thereof
CN106281182B (en) * 2016-08-09 2019-04-02 双成森工科技(北京)有限公司 Wood-based plate aqueous polyurethane is without aldehyde glue
CN106433529B (en) * 2016-09-21 2018-10-23 德华兔宝宝装饰新材股份有限公司 A kind of environment-friendly toughened adhesive of recombinant decorative timber-used and its application
CN106479306B (en) * 2016-09-21 2019-05-24 德华兔宝宝装饰新材股份有限公司 A kind of environment-friendly toughened adhesive
CN106336839B (en) * 2016-09-21 2018-06-29 德华兔宝宝装饰新材股份有限公司 A kind of preparation method for recombinating timber-used adhesive
WO2018058542A1 (en) * 2016-09-30 2018-04-05 张爱丽 Environmentally-friendly plastic material and manufacturing method thereof
CN110791227A (en) * 2019-11-28 2020-02-14 河南师范大学 Preparation process of environment-friendly plate glue

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CN1110296A (en) * 1994-04-13 1995-10-18 北京万事通电子技术有限公司 Method for preparation of adhesives by using maize starch
CN1876747A (en) * 2006-07-10 2006-12-13 武汉理工大学 Formaldehyde-free aqueous adhesive and preparing method thereof
WO2009074006A1 (en) * 2007-11-22 2009-06-18 National Starch And Chemical Investment Holding Corporation An adhesive, preparation and use thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1110296A (en) * 1994-04-13 1995-10-18 北京万事通电子技术有限公司 Method for preparation of adhesives by using maize starch
CN1876747A (en) * 2006-07-10 2006-12-13 武汉理工大学 Formaldehyde-free aqueous adhesive and preparing method thereof
WO2009074006A1 (en) * 2007-11-22 2009-06-18 National Starch And Chemical Investment Holding Corporation An adhesive, preparation and use thereof

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Effective date of registration: 20190116

Address after: No. 28, Xiangjiang Decoration Material Market East District, Xiangshan District, Guilin City, Guangxi Zhuang Autonomous Region

Patentee after: Guilin Xinmei Environmental Technology Co. Ltd.

Address before: Room 502, Building 4, No. 37 Tiexierli, Xiangshan District, Guilin City, Guangxi Zhuang Autonomous Region

Patentee before: Wang Qiansheng