CN101486889B - Monomer copolymerization modified soy protein adhesive and preparation thereof - Google Patents
Monomer copolymerization modified soy protein adhesive and preparation thereof Download PDFInfo
- Publication number
- CN101486889B CN101486889B CN2009100245775A CN200910024577A CN101486889B CN 101486889 B CN101486889 B CN 101486889B CN 2009100245775 A CN2009100245775 A CN 2009100245775A CN 200910024577 A CN200910024577 A CN 200910024577A CN 101486889 B CN101486889 B CN 101486889B
- Authority
- CN
- China
- Prior art keywords
- soybean protein
- reaction
- hour
- protein
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a monomer copolymerization modified soybean protein adhesive and a preparation method thereof; the monomer copolymerization modified soybean protein adhesive is essentially used in wood plywood production and furniture manufacturing, which belongs to the technical field of wood adhesive. The monomer copolymerization modified soybean protein adhesive has the above chemicalstructure, in which R is the polypeptide chain main chain of soybean protein, and n equals to the positive integer of 1, 2 until 20.
Description
Technical field
The present invention relates to a kind of monomer copolymerization modified soy protein adhesive and preparation method thereof, mainly be used in production of wood gluing plate and furniture and make, belong to the wood adhesive technical field.
Technical background
Protein is the important biomacromolecule of a class, cheap, with protein as renewable resources prepare biodegradable, biocompatible environment-friendly material is an emerging topic, in the material field, the soy-protein source is the abundantest, application potential is big, is described as " gold of growing ".
As far back as nineteen twenty-three, people such as O.Johnson just propose the basic theories that dregs of beans is made sizing agent, thereby have stepped the first step of soybean albumen adhesive development.The sixties in the thirties in 20th century to 20th century, because of soyflour wide material sources, advantage such as cheap, renewable, the soybean protein base adhesive is widely used in wood industry.But the bonding Wood products of soya-based sizing agent has been compared certain difference with the product that phenolic glue, urea-formaldehyde glue are bonding on bonding strength and water resistance.Therefore, after the sixties in 20th century, the rubber made from soybean cake stick progressively is synthesized the resin sizing agent and substitutes.In recent years, along with market to the restriction of the increase of sizing agent consumption demand, petroleum chemicals resource and to the environmental problem growing interest, make environmentally friendly sizing agent renewable, with low cost more and more be subject to people's attention.Soybean protein gluing agent thereby be subjected to people's attention again, main research work is how to improve the adhesive strength and the water resistance of tackiness agent now.
Discover, soybean protein is carried out modification handle, can improve the bonding strength and the water tolerance of soya-based sizing agent.Soy proteinaceous method of modifying has chemical modification, physically modified, enzyme-modified etc.
In order to give soybean albumen adhesive excellent water tolerance energy and bonding strength, a lot of methods are disclosed so far, as by in handling the soybean protein process, adding properties-correcting agent such as alkali, urea, make the secondary structure of soybean protein change, thereby improve the water tolerance of soybean albumen adhesive.(publication number: CN1912043), proposed a kind of method with the low alkali number tackiness agent of sodium-hydroxide treatment bean powder preparation, the tackiness agent of preparation can be used for adhesive bonding of wood at the Chinese invention patent ublic specification of application.At Chinese invention patent ublic specification of application (publication number: CN1793269), introduced with urea, sodium polyphosphate chemically modified soybean protein and prepared formaldehydeless volatilization, can not cause the soybean albumen adhesive of environmental pollution.More than two kinds of methods just introduced tackiness agent gummed intensity and the water-proof effect of improving for example, do not relate to the chemical reaction of properties-correcting agent and soybean protein.(publication number: CN101130678), provide a kind of aquosity polymer isocyanic ester adhesion agent of soy protein, the linking agent of selecting for use in tackiness agent is a polyisocynate monomer at the Chinese invention patent ublic specification of application.As everyone knows, the isocyanic ester raw materials cost is higher, is unfavorable for the widespread use of soybean albumen adhesive.
Summary of the invention
The objective of the invention is provides a kind of monomer copolymerization modified soy protein adhesive and preparation method thereof at above-mentioned weak point: select reaction monomers MALEIC ANHYDRIDE, vinylbenzene and soybean protein generation grafting and copolyreaction for use; Select monomer with low cost for use, preparation water resistance and bonding strength all reach the soybean albumen adhesive of respective country standard.
For realizing that the technical scheme that purpose of the present invention adopts is: utilize abundant soybean protein resource, select for use monomer with low cost that it is carried out modification, thereby prepare monomer-grafted soybean albumen adhesive to the soy-protein main chain.
Soybean albumen adhesive provided by the invention has following chemical structure:
Wherein R is the polypeptide chain main chain of soybean protein, n=1,2 ... 20 positive integer
Concrete preparation method is as follows for a kind of monomer copolymerization modified soy protein adhesive and preparation method thereof:
1. the soybean protein of 12～20 weight parts and the water of 100 weight parts are joined in the reaction vessel, wherein water is solvent, be warming up to 25 ℃ after, add the Sodium dodecylbenzene sulfonate of 0.3～0.5 weight part again; Temperature of reaction is risen to 50 ℃ from 25 ℃, adopt agitator to stir simultaneously 2～4 hours, carry out the modification of soybean protein, generate modified soy protein, after the Sodium dodecylbenzene sulfonate modification, make the hydrophobic side of soybean protein inside outwards transfer, thereby increase proteic surface hydrophobicity;
2. add the MALEIC ANHYDRIDE of 1～3 weight part in the above-mentioned modified soy protein, carry out graft reaction, generate MALEIC ANHYDRIDE grafting soybean protein.
3. after graft reaction carries out 1 hour, feed nitrogen in reaction vessel, air is wherein fallen in displacement; The reaction monomers vinylbenzene that adds 6～12 weight parts after half an hour adds the initiator ammonium persulfate of 0.12 weight part simultaneously, and temperature of reaction is risen to 70～90 ℃; React after 1 hour, add the vinylbenzene of 6～12 weight parts again, add the initiator ammonium persulfate of 0.28～0.4 weight part simultaneously.Vinylbenzene begins to generate multipolymer with MALEIC ANHYDRIDE grafting soybean protein generation copolyreaction.
4. after copolyreaction is carried out 1～2 hour, add the initiator ammonium persulfate of 0.1～0.3 weight part, further reacted 1～2 hour, make remaining reaction monomers react completely, prepare a kind of monomer copolymerization modified soy protein adhesive.
Soybean protein described in the present invention is selected a kind of in soyflour, soybean protein isolate or the low temperature soy meal for use.
Chemical equation of the present invention has:
The first step: soy-protein and maleic acid anhydride reactant
Second step: graft product and vinylbenzene generation copolyreaction
The characteristics of the monomer polymerization modified soy protein adhesive that the present invention prepares are: with renewable resources---soybean protein is a raw material, utilize monomer with low cost that the soybean protein main chain is carried out graft polymerization, and then synthesize a kind of novel soybean albumen adhesive, obtain the deep processed product of soybean protein, improved the added value of soybean protein.
The present invention:
1. synthetic new water resistance and the good soybean albumen adhesive of bonding strength of a class that obtained;
2. invent out a kind of synthetic method, make on the synthetic soybean albumen adhesive main chain that obtains other polymkeric substance in the grafting;
3. selected monomer is with low cost, helps the practical application and the popularization of product;
4. can not volatilize formaldehyde, the poisonous and hazardous material of phenol of tackiness agent, sizing agent environmental protection in the process of using, health can be applied to fields such as wood gluing plate, shaving board, fiberboard.
Embodiment
Following specific embodiment is to further specify of the present invention, rather than limits the scope of the invention.
A kind of monomer copolymerization modified soy protein adhesive and preparation method thereof:
Embodiment 1,
1. the soyflour of 16g and the water of 100g are joined in the reaction vessel, wherein water is solvent, be warming up to 25 ℃ after, add the Sodium dodecylbenzene sulfonate of 0.3g again; Temperature of reaction is warming up to 50 ℃ from 25 ℃, stirred 2 hours, carry out the modification of soybean protein, generate modified soy protein, by Sodium dodecylbenzene sulfonate modification soybean protein wherein, make protein interior hydrophobic side then outwards, thereby increase proteinic surface hydrophobicity.
2. the MALEIC ANHYDRIDE that adds 2g in the above-mentioned modified soy protein, reaction generate MALEIC ANHYDRIDE grafting soybean protein.
3. after graft reaction carries out 1 hour, feed nitrogen, the air in the reaction vessel is fallen in displacement; Add the reaction monomers vinylbenzene of 6g and the initiator ammonium persulfate of 0.12g after half an hour, be warming up to 80 ℃ simultaneously; React the styrene monomer that adds 6g after 1 hour, add the ammonium persulphate of 0.34g simultaneously, vinylbenzene begins to generate multipolymer with MALEIC ANHYDRIDE grafting soybean protein generation copolyreaction.
4. copolyreaction adds the ammonium persulphate of 0.3g after 1 hour again, continues reaction after 1.5 hours, and reaction finishes, and makes remaining reaction monomers react completely, and prepares monomer copolymerization modified soy protein adhesive.
After testing: the tackiness agent outward appearance is a milky white liquid, solid content is 24.5%, contact angle on the board using poplar board surface is: 36 °, recording viscosity with rotational viscosimeter is 195mPa.S, by in the mensuration of GB GB9846.12 glued board gummed intensity about the measuring method of I, II, IV class glued board, the intensity of the bonding board using poplar board of tackiness agent is respectively: 1.921MPa, 2.404MPa, 2.813MPa all obviously surpass the value (0.7MPa) that standard GB/T9846.3 stipulates.
Embodiment 2,
1. the soyflour of 12g and the water of 100g are joined in the reaction vessel, wherein water is solvent, be warming up to 25 ℃ after, add the Sodium dodecylbenzene sulfonate of 0.5g again; Temperature of reaction is warming up to 50 ℃ from 25 ℃, stirred 3 hours, carry out the modification of soybean protein, generate modified soy protein, by Sodium dodecylbenzene sulfonate modification soybean protein wherein, make protein interior hydrophobic side then outwards, thereby increase proteinic surface hydrophobicity.
2. the MALEIC ANHYDRIDE that adds 3g in the above-mentioned modified soy protein, reaction generate MALEIC ANHYDRIDE grafting soybean protein.
3. after graft reaction carries out 1 hour, feed nitrogen, the air in the reaction vessel is fallen in displacement; Add the reaction monomers vinylbenzene of 12g and the initiator ammonium persulfate of 0.12g after half an hour, be warming up to 70 ℃ simultaneously; React the styrene monomer that adds 9g after 1 hour, add the ammonium persulphate of 0.28g simultaneously, vinylbenzene begins to generate multipolymer with MALEIC ANHYDRIDE grafting soybean protein generation copolyreaction.
4. copolyreaction adds the ammonium persulphate of 0.2g after 2 hours again, continues reaction after 1 hour, and reaction finishes, and makes remaining reaction monomers react completely, and prepares monomer copolymerization modified soy protein adhesive.
After testing: the tackiness agent outward appearance is a milky white liquid, solid content is 25.8%, contact angle on the board using poplar board surface is: 38 °, recording viscosity with rotational viscosimeter is 231mPa.S, by in the mensuration of GB GB9846.12 glued board gummed intensity about the measuring method of I, II, IV class glued board, the intensity of the bonding board using poplar board of tackiness agent is respectively: 1.856MPa, 2.405MPa, 3.112MPa all obviously surpass the value (0.7MPa) that standard GB/T9846.3 stipulates.
Embodiment 3,
1. the soybean protein isolate of 20g and the water of 100g are joined in the reaction vessel, wherein water is solvent, be warming up to 25 ℃ after, add the Sodium dodecylbenzene sulfonate of 0.4g again; Temperature of reaction is warming up to 50 ℃ from 25 ℃, stirred 4 hours, carry out the modification of soybean protein, generate modified soy protein, by Sodium dodecylbenzene sulfonate modification soybean protein wherein, make protein interior hydrophobic side then outwards, thereby increase proteinic surface hydrophobicity.
2. the MALEIC ANHYDRIDE that adds 3g in the above-mentioned modified soy protein, reaction generate MALEIC ANHYDRIDE grafting soybean protein.
3. after graft reaction carries out 1 hour, feed nitrogen, the air in the reaction vessel is fallen in displacement; Add the reaction monomers vinylbenzene of 12g and the ammonium persulphate of 0.12g after half an hour, be warming up to 90 ℃ simultaneously; React the styrene monomer that adds 12g after 1 hour, add the ammonium persulphate of 0.4g simultaneously, vinylbenzene begins to generate multipolymer with MALEIC ANHYDRIDE grafting soybean protein generation copolyreaction.
4. copolyreaction adds the ammonium persulphate of 0.3g after 2 hours, continues reaction after 2 hours, and reaction finishes, and makes remaining reaction monomers react completely, and prepares monomer copolymerization modified soy protein adhesive.
After testing: the tackiness agent outward appearance is a milky white liquid, solid content is 28.9%, contact angle on the board using poplar board surface is: 35 °, recording viscosity with rotational viscosimeter is 243mPa.S, by in the mensuration of GB GB9846.12 glued board gummed intensity about the measuring method of I, II, IV class glued board, the intensity of the bonding board using poplar board of tackiness agent is respectively: 2.104MPa, 2.252MPa, 2.925MPa all obviously surpass the value (0.7MPa) that standard GB/T9846.3 stipulates.
Embodiment 4,
1. the soybean protein isolate of 16g and the water of 100g are joined in the reaction vessel, wherein water is solvent, be warming up to 25 ℃ after, add the Sodium dodecylbenzene sulfonate of 0.4g again; Temperature of reaction is warming up to 50 ℃ from 25 ℃, stirred 3 hours, carry out the modification of soybean protein, generate modified soy protein, by Sodium dodecylbenzene sulfonate modification soybean protein wherein, make protein interior hydrophobic side then outwards, thereby increase proteinic surface hydrophobicity.
2. the MALEIC ANHYDRIDE that adds 3g in the above-mentioned modified soy protein, reaction generate MALEIC ANHYDRIDE grafting soybean protein.
3. after graft reaction carries out 1 hour, feed nitrogen, the air in the reaction vessel is fallen in displacement; Add the reaction monomers vinylbenzene of 12g and the initiator ammonium persulfate of 0.12g after half an hour, be warming up to 80 ℃ simultaneously; React the styrene monomer that adds 9g after 1 hour, add the ammonium persulphate of 0.4g simultaneously, vinylbenzene begins to generate multipolymer with MALEIC ANHYDRIDE grafting soybean protein generation copolyreaction.
4. copolyreaction carries out adding after 1.5 hours the ammonium persulphate of 0.2g, continues reaction after 1 hour, and reaction finishes, and makes remaining reaction monomers react completely, and prepares monomer copolymerization modified soy protein adhesive.
After testing: the tackiness agent outward appearance is a milky white liquid, solid content is 27.8%, contact angle on the board using poplar board surface is: 39 °, recording viscosity with rotational viscosimeter is 278mPa.S, by in the mensuration of GB GB9846.12 glued board gummed intensity about the measuring method of I, II, IV class glued board, the intensity of the bonding board using poplar board of tackiness agent is respectively: 1.885MPa, 2.312MPa, 2.902MPa all obviously surpass the value (0.7MPa) that standard GB/T9846.3 stipulates.
Embodiment 5,
1. the low temperature soy meal of 12g and the water of 100g are joined in the reaction vessel, wherein water is solvent, be warming up to 25 ℃ after, add the Sodium dodecylbenzene sulfonate of 0.5g again; Temperature of reaction is warming up to 50 ℃ from 25 ℃, stirred 2 hours, carry out the modification of soybean protein, generate modified soy protein, by Sodium dodecylbenzene sulfonate modification soybean protein wherein, make protein interior hydrophobic side then outwards, thereby increase proteinic surface hydrophobicity.
2. the MALEIC ANHYDRIDE that adds 1g in the above-mentioned modified soy protein, reaction generate MALEIC ANHYDRIDE grafting soybean protein.
3. after graft reaction carries out 1 hour, feed nitrogen, the air in the reaction vessel is fallen in displacement; Add the reaction monomers vinylbenzene of 9g and the initiator ammonium persulfate of 0.12g after half an hour, be warming up to 70 ℃ simultaneously; React the styrene monomer that adds 12g after 1 hour, add the ammonium persulphate of 0.34g simultaneously, vinylbenzene begins to generate multipolymer with MALEIC ANHYDRIDE grafting soybean protein generation copolyreaction.
4. copolyreaction carries out adding after 1.5 hours the ammonium persulphate of 0.3g, continues reaction after 2 hours, and reaction finishes, and makes remaining reaction monomers react completely, and prepares monomer copolymerization modified soy protein adhesive.
After testing: the tackiness agent outward appearance is a milky white liquid, solid content is 27.5%, contact angle on the board using poplar board surface is: 31 °, recording viscosity with rotational viscosimeter is 135mPa.S, by in the mensuration of GB GB9846.12 glued board gummed intensity about the measuring method of I, II, IV class glued board, the intensity of the bonding board using poplar board of tackiness agent is respectively: 1.855MPa, 2.326MPa, 2.852MPa all obviously surpass the value (0.7MPa) that standard GB/T9846.3 stipulates.
Embodiment 6,
1. the low temperature soy meal of 20g and the water of 100g are joined in the reaction vessel, wherein water is solvent, be warming up to 25 ℃ after, add the Sodium dodecylbenzene sulfonate of 0.5g again; Temperature of reaction is warming up to 50 ℃ from 25 ℃, stirred 4 hours, carry out the modification of soybean protein, generate modified soy protein, by Sodium dodecylbenzene sulfonate modification soybean protein wherein, make protein interior hydrophobic side then outwards, thereby increase proteinic surface hydrophobicity.
2. the MALEIC ANHYDRIDE that adds 3g in the above-mentioned modified soy protein, reaction generate MALEIC ANHYDRIDE grafting soybean protein.
3. after graft reaction carries out 1 hour, feed nitrogen, the air in the reaction vessel is fallen in displacement; Add the reaction monomers vinylbenzene of 12g and the initiator ammonium persulfate of 0.12g after half an hour, be warming up to 90 ℃ simultaneously; React the styrene monomer that adds 6g after 1 hour, add the ammonium persulphate of 0.4g simultaneously, vinylbenzene begins to generate multipolymer with MALEIC ANHYDRIDE grafting soybean protein generation copolyreaction.
4. copolyreaction carries out adding after 2 hours the ammonium persulphate of 0.1g, continues reaction after 1 hour, and reaction finishes, and makes remaining reaction monomers react completely, and prepares monomer copolymerization modified soy protein adhesive.
After testing: the tackiness agent outward appearance is a milky white liquid, solid content is 26.6%, contact angle on the board using poplar board surface is: 34 °, recording viscosity with rotational viscosimeter is 289mPa.S, by in the mensuration of GB GB9846.12 glued board gummed intensity about the measuring method of I, II, IV class glued board, the intensity of the bonding board using poplar board of tackiness agent is respectively: 2.098MPa, 2.432MPa, 3.342MPa all obviously surpass the value (0.7MPa) that standard GB/T9846.3 stipulates.
Claims (2)
1. the preparation method of a monomer copolymerization modified soy protein adhesive is characterized in that
The preparation method is as follows:
(1) soybean protein of 12～20 weight parts and the water of 100 weight parts are joined in the reaction vessel, wherein water is solvent, be warming up to 25 ℃ after, add the Sodium dodecylbenzene sulfonate of 0.3～0.5 weight part again; Temperature of reaction is risen to 50 ℃ from 25 ℃, adopt agitator to stir simultaneously 2～4 hours, carry out the modification of soybean protein, generate modified soy protein, after the Sodium dodecylbenzene sulfonate modification, make the hydrophobic side of soybean protein inside outwards transfer, thereby increase proteic surface hydrophobicity;
(2) add the MALEIC ANHYDRIDE of 1～3 weight part in the above-mentioned modified soy protein, carry out graft reaction, generate MALEIC ANHYDRIDE grafting soybean protein;
(3) after graft reaction carries out 1 hour, feed nitrogen in reaction vessel, air is wherein fallen in displacement; The reaction monomers vinylbenzene that adds 6～12 weight parts after half an hour adds the initiator ammonium persulfate of 0.12 weight part simultaneously, and temperature of reaction is risen to 70～90 ℃; React after 1 hour, add the vinylbenzene of 6～12 weight parts again, add the initiator ammonium persulfate of 0.28～0.4 weight part simultaneously, vinylbenzene begins to generate multipolymer with MALEIC ANHYDRIDE grafting soybean protein generation copolyreaction;
(4) after copolyreaction is carried out 1～2 hour, add the initiator ammonium persulfate of 0.1～0.3 weight part, further reacted 1～2 hour, make remaining reaction monomers react completely, prepare a kind of monomer copolymerization modified soy protein adhesive.
2. the preparation method of a kind of monomer copolymerization modified soy protein adhesive according to claim 1 is characterized in that described soybean protein selects a kind of in soyflour, soybean protein isolate or the low temperature soy meal for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100245775A CN101486889B (en) | 2009-02-20 | 2009-02-20 | Monomer copolymerization modified soy protein adhesive and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100245775A CN101486889B (en) | 2009-02-20 | 2009-02-20 | Monomer copolymerization modified soy protein adhesive and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101486889A CN101486889A (en) | 2009-07-22 |
| CN101486889B true CN101486889B (en) | 2010-12-29 |
Family
ID=40889955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100245775A Expired - Fee Related CN101486889B (en) | 2009-02-20 | 2009-02-20 | Monomer copolymerization modified soy protein adhesive and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101486889B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086371B (en) * | 2010-11-19 | 2013-04-24 | 南京林业大学 | Method for preparing antiseptic soy protein adhesive |
| CN103666342B (en) * | 2013-12-26 | 2016-03-02 | 北华大学 | The preparation method of acrylic amide modified soybean protein composite adhesive |
| CN103881652B (en) * | 2014-02-26 | 2017-09-29 | 南京工业大学 | Silane coupling agent enhanced modified bean cake based adhesive and preparation method thereof |
| CN107418508A (en) * | 2017-09-21 | 2017-12-01 | 南通盛赫园林古建筑工程有限公司 | A kind of high-intensity wood product cementing agent |
| CN108748452A (en) * | 2018-06-07 | 2018-11-06 | 安徽宏润工艺品有限公司 | A method of preparing water-fast weather-proof bamboo flooring with biochemical modified soybean albumen adhesive |
| CN109294487A (en) * | 2018-09-08 | 2019-02-01 | 佛山朝鸿新材料科技有限公司 | A kind of preparation method of high stable water-resistant type white glue with vinyl |
-
2009
- 2009-02-20 CN CN2009100245775A patent/CN101486889B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101486889A (en) | 2009-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101486889B (en) | Monomer copolymerization modified soy protein adhesive and preparation thereof | |
| CN100556974C (en) | A kind of aqueous adhesive without aldehyde and preparation method thereof | |
| CN101497778B (en) | Preparation of epoxy resin modified soy protein adhesive | |
| CN101831255B (en) | Method for preparing modified starch adhesive for timber | |
| CN104774588A (en) | Protein-based wood adhesive, and preparation method and application and use method thereof | |
| CN108359407B (en) | Modified vegetable protein adhesive and preparation method thereof | |
| CN101649179A (en) | Modified soybean-based adhesive and preparation method thereof | |
| CN103865477A (en) | Crosslinked modified soybean protein adhesive | |
| CN109370512A (en) | A kind of glued board walnut cake protein adhesive and preparation method thereof | |
| CN107641495A (en) | A kind of vegetable protein adhesive and its preparation method and application | |
| CN102533182A (en) | Method for preparing starch-based water-resistant adhesive for corrugated board production | |
| CN104178083A (en) | Formaldehyde-free bean-pulp-base artificial board adhesive and preparation method thereof | |
| CN111234132B (en) | Water-based epoxy resin cross-linking agent, modified protein adhesive and application | |
| CN102690615B (en) | Polystyrene waterproof wood adhesive | |
| CN106827161A (en) | A kind of preparation method without aldehyde bamboo shaving plate | |
| CN103952118A (en) | Modified soybean protein adhesive and preparation method thereof | |
| CN116589976A (en) | Waterproof peony seed meal wood adhesive and preparation method thereof | |
| CN102399515B (en) | Curing agent for protein adhesive, and preparation method and application of curing agent | |
| CN108794712A (en) | A kind of modified urea-formaldehyde resin preparation method used for bottom plate of container | |
| CN101979452B (en) | Method for preparing waterproof adhesive for corrugated paper production | |
| CN103694932A (en) | Modified soybean-based emulsion adhesive and preparation method thereof | |
| CN110003493A (en) | In-situ modified dregs of beans, adhesive and the preparation method and application thereof | |
| CN110437766A (en) | A kind of no aldehyde low cost polysaccharide adhesive and preparation method thereof | |
| CN113652196B (en) | Formaldehyde-free soybean glue and preparation method and application thereof | |
| CN118185527B (en) | 502 Glue composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Danyang Xinmeilong Automobile Soft Trim Co.,Ltd. Assignor: Nanjing Forestry University Contract record no.: 2012320000112 Denomination of invention: Monomer copolymerization modified soy protein adhesive and preparation thereof Granted publication date: 20101229 License type: Exclusive License Open date: 20090722 Record date: 20120227 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101229 Termination date: 20120220 |