CN111171256A - Modified isocyanate emulsion crosslinking agent, modified adhesive and application - Google Patents
Modified isocyanate emulsion crosslinking agent, modified adhesive and application Download PDFInfo
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- CN111171256A CN111171256A CN202010066314.7A CN202010066314A CN111171256A CN 111171256 A CN111171256 A CN 111171256A CN 202010066314 A CN202010066314 A CN 202010066314A CN 111171256 A CN111171256 A CN 111171256A
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- Prior art keywords
- isocyanate
- modified
- modifier
- parts
- crosslinking agent
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- Granted
Links
- 239000012948 isocyanate Substances 0.000 title claims abstract description 104
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 104
- 239000000853 adhesive Substances 0.000 title claims abstract description 81
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 81
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 57
- 239000000839 emulsion Substances 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 108010082495 Dietary Plant Proteins Proteins 0.000 claims abstract description 53
- 239000003607 modifier Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 12
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 12
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000012054 meals Nutrition 0.000 claims description 51
- 235000018102 proteins Nutrition 0.000 claims description 44
- 108090000623 proteins and genes Proteins 0.000 claims description 44
- 102000004169 proteins and genes Human genes 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 22
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 16
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 10
- 239000001263 FEMA 3042 Substances 0.000 claims description 10
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 10
- 235000004515 gallic acid Nutrition 0.000 claims description 10
- 229940074391 gallic acid Drugs 0.000 claims description 10
- 229920002258 tannic acid Polymers 0.000 claims description 10
- 235000015523 tannic acid Nutrition 0.000 claims description 10
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 10
- 229940033123 tannic acid Drugs 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000002023 wood Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 241000196324 Embryophyta Species 0.000 claims description 4
- 102000035118 modified proteins Human genes 0.000 claims description 4
- 108091005573 modified proteins Proteins 0.000 claims description 4
- -1 polymethylene Polymers 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 239000004971 Cross linker Substances 0.000 claims description 3
- 244000082204 Phyllostachys viridis Species 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 241000208140 Acer Species 0.000 claims description 2
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 2
- 244000105624 Arachis hypogaea Species 0.000 claims description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 2
- 235000018262 Arachis monticola Nutrition 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 2
- 108010064851 Plant Proteins Proteins 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 235000019779 Rapeseed Meal Nutrition 0.000 claims description 2
- 235000004443 Ricinus communis Nutrition 0.000 claims description 2
- 244000269722 Thea sinensis Species 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 238000005034 decoration Methods 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000020232 peanut Nutrition 0.000 claims description 2
- 235000021118 plant-derived protein Nutrition 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 239000004456 rapeseed meal Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920001864 tannin Polymers 0.000 claims description 2
- 235000018553 tannin Nutrition 0.000 claims description 2
- 239000001648 tannin Substances 0.000 claims description 2
- 235000013616 tea Nutrition 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 244000046052 Phaseolus vulgaris Species 0.000 claims 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 15
- 238000003825 pressing Methods 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000007731 hot pressing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011120 plywood Substances 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- 235000019764 Soybean Meal Nutrition 0.000 description 2
- 108010073771 Soybean Proteins Proteins 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011094 fiberboard Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000004455 soybean meal Substances 0.000 description 2
- 235000019710 soybean protein Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- 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
- 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
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a modified isocyanate emulsion crosslinking agent, a modified adhesive and application. The modified isocyanate crosslinking agent is prepared by polymerizing a modifying agent and isocyanate; wherein the modifier contains a catechol group. The embodiment of the invention also provides a modified vegetable protein adhesive prepared from the modified isocyanate emulsion crosslinking agent. According to the invention, the polyphenol substance containing the catechol group is polymerized with the isocyanate, so that the stability of the isocyanate can be improved, and when the polyphenol substance is used for preparing the vegetable protein adhesive, the prepressing performance of the adhesive can be improved, and meanwhile, the water resistance and the bonding strength of the adhesive can be effectively enhanced.
Description
Technical Field
The invention relates to a vegetable protein adhesive, in particular to a modified isocyanate emulsion crosslinking agent, a modified adhesive and application.
Background
The vegetable protein adhesive is an effective substitute for the trialdehyde adhesive, and becomes a hotspot for the research of the wood processing industry due to the advantages of no formaldehyde release, rich sources, simple preparation process and the like. The soybean protein, polysaccharide and the like have large molecular weight, and the viscosity of the adhesive is high after the soybean protein, polysaccharide and the like are dissolved. In order to ensure good flowability of the adhesive, the solid content is generally low; therefore, the problem of poor pre-pressing forming performance is easily caused in the processing process, and the pre-pressing forming processing of the artificial board is not facilitated.
The emulsion cross-linking agent prepared by emulsifying isocyanate and water is added into the vegetable protein adhesive, so that the pre-pressing forming performance and the water-resistant bonding strength can be effectively improved. The high-reactivity isocyanate is used as an auxiliary crosslinking agent to modify the vegetable protein adhesive, and a covalent crosslinking structure is formed among the isocyanate, the vegetable protein and the wood, so that the normal-temperature pre-pressing forming performance of the adhesive is obviously improved. However, the isocyanate reacts with water at normal temperature to generate carbon dioxide, so that the system is easy to foam and short in working life, and the industrial actual production requirement is difficult to meet.
In order to prolong the working life of the isocyanate modified waterborne adhesive, a great deal of related research is carried out. The conventional modification method is to add a filler into isocyanate or adopt a chemical blocking method to improve the stability of the isocyanate, but the conventional modification method has the problems of uneven dispersion, easy stress concentration of an adhesive layer, complex process and the like, and is limited in practical use. How to simultaneously ensure the gluing performance and the prepressing forming performance of the adhesive and meet the production requirements becomes a main problem faced by the modified vegetable protein adhesive.
Disclosure of Invention
The inventor finds that the stability of isocyanate can be improved by polymerizing the polyphenol substance containing the catechol group with the isocyanate, and the application of the polyphenol substance containing the catechol group in the preparation of the vegetable protein adhesive can improve the prepressing performance of the adhesive and the forming performance of the adhesive in the process of adhering the veneer with high water content, and can effectively enhance the water resistance and the adhesive strength of the adhesive.
The embodiment of the invention provides a modified isocyanate crosslinking agent which is prepared by polymerizing a modifying agent and isocyanate.
In some embodiments of the invention, the modifier contains a catechol group.
In some embodiments of the invention, the modifying agent is a polyphenol, such as a plant polyphenol, that contains catechol groups.
In some embodiments of the invention, the modifying agent is selected from one or more of tannic acid, tannins, tea polyphenols, gallic acid and the like.
In some embodiments of the present invention, the isocyanate is selected from one or more mixtures of polymeric diphenylmethane diisocyanate (pMDI), isophorone diisocyanate (IPDI), triphenylmethane triisocyanate, polyphenyl polymethylene polyisocyanates, TDI-tricyanomethylpropane adducts, and the like.
In some embodiments of the invention, the isocyanate is polymeric diphenylmethane diisocyanate (pMDI), wherein the-NCO group content is 31.6%.
In some embodiments of the invention, the weight ratio of modifier to isocyanate is (2-8): 20.
In some embodiments of the invention, the weight ratio of modifier to isocyanate is (3.5-5): 20.
In some embodiments of the invention, the weight ratio of modifier to isocyanate is (4-5): 20.
In some embodiments of the present invention, the modified isocyanate crosslinking agent is prepared by polymerizing a modifying agent with an isocyanate in the presence of water. In some embodiments of the invention, the weight ratio of water to isocyanate is (5-15):20, preferably (6-8): 20.
In some embodiments of the invention, the modified isocyanate crosslinker is an emulsion.
The embodiment of the invention also provides a modified isocyanate emulsion crosslinking agent which is prepared from the following raw materials in parts by weight:
isocyanate 20 parts
5-15 parts of water
2-8 parts of modifier
In some embodiments of the present invention, the modified isocyanate emulsion crosslinking agent is prepared from the following raw materials in parts by weight:
isocyanate 20 parts
6-8 parts of water
3.5 to 5 portions of modifier
In some embodiments of the present invention, the modified isocyanate emulsion crosslinking agent is prepared from the following raw materials in parts by weight:
isocyanate 20 parts
6-8 parts of water
4-5 parts of modifier
In some embodiments of the present invention, the isocyanate and the modifier in the modified isocyanate emulsion crosslinking agent are as defined above.
The modified isocyanate crosslinking agent and the modified isocyanate emulsion crosslinking agent provided by the embodiment of the invention have high stability and good reaction activity, and can improve the pre-pressing forming performance, water resistance and bonding strength when the plant protein adhesive is bonded with a veneer with high water content. In addition, the preparation process has the advantages of simplicity and convenience.
The embodiment of the invention also provides a preparation method of the modified isocyanate crosslinking agent, which comprises the step of polymerizing the modifying agent and isocyanate. In some embodiments, the polymerization is carried out in the presence of water.
The embodiment of the invention also provides a preparation method of the modified isocyanate emulsion crosslinking agent, which comprises the following steps:
1) providing an aqueous modifier solution;
2) mixing the aqueous modifier solution with isocyanate to polymerize the modifier with the isocyanate.
Wherein the content of the first and second substances,
the modifier aqueous solution in the step 1) is prepared from the modifier and water. Specifically, the modifier can be added to water (e.g., 50-80 deg.C hot water; in some embodiments 60 deg.C hot water) according to a certain ratio and stirred until the mixture is uniform, for example, 5-10 minutes (or 6 minutes). The mixing can be carried out by means of mechanical stirring, for example at a speed of 600 to 1200 rpm.
In some embodiments, step 2) further comprises the step of emulsifying after mixing the aqueous modifier solution with the isocyanate. The aqueous modifier solution can be uniformly mixed with the oily isocyanate matrix through emulsification to prepare the emulsion crosslinking agent with uniform texture.
In some embodiments, step 2) may be emulsified using an emulsifying machine for a period of time ranging from 5 to 15 minutes, such as 8 minutes.
The invention also comprises the modified isocyanate emulsion crosslinking agent prepared by the method.
The invention also provides an application of the modified isocyanate crosslinking agent or the modified isocyanate emulsion crosslinking agent in preparation of a vegetable protein adhesive. Experiments show that the vegetable protein adhesive prepared by the modified isocyanate crosslinking agent and the modified isocyanate emulsion crosslinking agent has the advantages of higher bonding strength, good water resistance, no formaldehyde release, good pre-pressing forming performance and the like.
The invention also provides a modified vegetable protein adhesive which is prepared from the following raw materials in parts by weight:
in some embodiments of the invention, the protein meal is vegetable protein meal.
In some embodiments of the present invention, the protein meal is one or more of soybean meal, maple meal, peanut meal, castor meal, cottonseed meal, rapeseed meal, distillers' grains, and the like.
In some embodiments of the invention, the protein meal has a particle size of 70-500 mesh.
In some embodiments of the invention, the protein meal has a particle size of 100-400 mesh.
In some embodiments of the invention, the protein meal has a particle size of 200-250 mesh.
The protein meal in the particle size range is powdery, and the powder is easy to disperse and is beneficial to full contact and reaction with the cross-linking agent.
In some embodiments of the invention, the protein meal is defatted protein meal.
In some embodiments of the invention, the protein content of the protein meal is greater than 40 wt%.
In some embodiments of the invention, the protein content of the protein meal is 40-60 wt%.
In some embodiments of the invention, the protein content of the protein meal is 43 wt%.
In some embodiments of the present invention, the curing agent is a glycidyl ether, for example, one or more selected from polyamide polyamine epichlorohydrin resin (PAE), epoxy diluent glycerol triglycidyl ether (PTGE), ethylene glycol diglycidyl ether (EDGE), and other crosslinking agents, preferably PTGE.
In some embodiments of the present invention, the modified vegetable protein adhesive is prepared from the following raw materials in parts by weight:
in some embodiments of the present invention, the modified vegetable protein adhesive is prepared from the following raw materials in parts by weight:
in some embodiments of the present invention, the preparation method of the vegetable protein adhesive comprises the following steps:
a) providing a mixed solution containing protein meal and water;
b) and mixing the mixed solution containing the protein meal and the water with the modified isocyanate emulsion crosslinking agent and the curing agent to prepare the modified vegetable protein adhesive.
Wherein, the protein meal raw material can be added into water under the condition of stirring in the step a) and is uniformly stirred; to prepare a mixed solution containing protein meal and water.
And b) adding the modified isocyanate emulsion crosslinking agent and the curing agent into the mixed solution containing the protein meal and water, and stirring to obtain the modified vegetable protein adhesive.
In some embodiments of the present invention, the step a) and b) may be performed by mechanical stirring, for example, at a speed of 600-1200 rpm.
The invention also comprises the application of the modified vegetable protein adhesive in the fields of wood, bamboo, furniture, printed matters, buildings, decoration and the like.
In particular, the invention also comprises wood products and bamboo products containing the modified vegetable protein adhesive, such as artificial boards such as plywood, shaving board, medium density fiberboard and laminated wood board.
The preparation method of the modified isocyanate emulsion crosslinking agent provided by the embodiment of the invention adopts a method of directly emulsifying isocyanate and an aqueous solution, and the plant polyphenol is added into water and uniformly mixed, and then is emulsified with the isocyanate, so that the distribution of the plant polyphenol is more uniform, and the operation is simple.
The preparation method of the modified vegetable protein adhesive provided by the embodiment of the invention adopts a physical blending method, firstly, protein meal is dispersed into water, and is stirred uniformly to obtain unmodified vegetable protein adhesive, then, the modified isocyanate emulsion crosslinking agent and the curing agent are added into the vegetable protein adhesive, and the modified vegetable protein adhesive is obtained after being stirred uniformly. In the obtained vegetable protein glue, the isocyanate emulsion cross-linking agent and the curing agent are uniformly dispersed and tightly combined with protein molecules.
The modified protein adhesive prepared by the embodiment of the invention has no formaldehyde release, and the manufactured artificial board has no formaldehyde release problem; the adhesive strength is high, the water resistance is excellent, and the requirements of II-type plywood can be met; and because the modified isocyanate emulsion cross-linking agent is introduced into the vegetable protein adhesive, the vegetable protein adhesive has better pre-pressing forming performance even when a veneer with high water content is glued, is beneficial to the wood processing process for processing the board, and can be used for producing artificial boards such as plywood, shaving board, medium-density fiberboard, laminated wood board and the like.
The protein meal serving as the main raw material in the embodiment of the invention is grain crop processing residues, is a renewable resource, can simultaneously solve the problems of recycling of grain crop wastes and high cost of the biomass adhesive, solves the problem of excessive dependence of the synthetic adhesive on fossil resources, meets the requirements of environmental protection and sustainable development, and has important economic and social benefits.
The method provided by the embodiment of the invention is simple and feasible in process and is suitable for industrial production.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The protein meal used below is defatted soybean meal powder, contains more than or equal to 43% (w/w) of protein, and has a particle size of 200-250 meshes.
The curing agent used below was glycerol triglycidyl ether (PTGE).
Example 1
This example also provides a method for preparing the modified isocyanate emulsion crosslinking agent, comprising:
1. adding 4kg of tannic acid into 7kg of water, and stirring for 6 minutes by adopting a mechanical stirring method until the tannic acid is uniformly mixed to obtain a tannic acid water solution;
2. the prepared tannic acid aqueous solution is added into 20kg of pMDI to be directly emulsified for 10 minutes to obtain the uniform modified isocyanate emulsion crosslinking agent.
The embodiment provides a modified vegetable protein adhesive, which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified vegetable protein adhesive, which comprises the following steps:
1. dispersing 25kg of protein meal into 70kg of water, and uniformly stirring at the rotating speed of 800 revolutions per minute to obtain a mixed solution containing the protein meal and the water;
2. adding 8kg of the modified isocyanate emulsion crosslinking agent into a mixed solution containing protein meal and water under the stirring condition of the rotating speed of 900 revolutions per minute, and stirring for 5 minutes for later use;
3. and (3) adding 6kg of curing agent into the system obtained in the step (2), and stirring for 10 minutes to be uniform under the condition of the rotation speed of 900 revolutions per minute to obtain the modified vegetable protein adhesive.
Example 2
The embodiment provides a modified isocyanate emulsion crosslinking agent, which is prepared from the following raw materials in parts by weight:
this example also provides a method for preparing the modified isocyanate emulsion crosslinking agent, comprising:
1. adding 3.5kg of tannic acid into 8kg of water, and stirring for 5 minutes by adopting a mechanical stirring method until the tannic acid is uniformly mixed to obtain a tannic acid water solution;
2. the prepared tannic acid aqueous solution is added into 20kg of pMDI, and the mixture is directly emulsified for 8 minutes to obtain the uniform modified isocyanate emulsion crosslinking agent.
The embodiment provides a modified vegetable protein adhesive, which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified vegetable protein adhesive, which comprises the following steps:
1. dispersing 28kg of protein meal in 70kg of water, and uniformly stirring at the rotating speed of 900 revolutions per minute to obtain a mixed solution containing the protein meal and the water;
2. adding 5kg of the modified isocyanate emulsion crosslinking agent into a mixed solution containing protein meal and water under the stirring condition of the rotating speed of 900 revolutions per minute, and stirring for 6 minutes for later use;
3. and (3) adding 7kg of curing agent into the system obtained in the step (2), and stirring for 15 minutes at the rotating speed of 900 revolutions per minute until the curing agent is uniform, so as to obtain the modified vegetable protein adhesive.
Example 3
The embodiment provides a modified isocyanate emulsion crosslinking agent, which is prepared from the following raw materials in parts by weight:
this example also provides a method for preparing the modified isocyanate emulsion crosslinking agent, comprising:
1. adding 5kg of gallic acid into 7kg of water heated to 60 ℃, and stirring for 6 minutes by adopting a mechanical stirring method until the gallic acid is uniformly mixed to obtain a gallic acid aqueous solution;
2. adding the prepared gallic acid aqueous solution into 20kg of pMDI to directly emulsify for 15 minutes to obtain the uniform modified isocyanate emulsion crosslinking agent.
The embodiment provides a modified vegetable protein adhesive, which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified vegetable protein adhesive, which comprises the following steps:
1. dispersing 30kg of protein meal in 70kg of water, and uniformly stirring at the rotating speed of 900 revolutions per minute to obtain a mixed solution containing the protein meal and the water;
2. adding 8kg of the modified isocyanate emulsion crosslinking agent into a mixed solution containing protein meal and water under the stirring condition of the rotating speed of 900 revolutions per minute, and stirring for 5 minutes for later use;
3. and (3) adding 6kg of curing agent into the system obtained in the step (2), and stirring for 12 minutes at the rotating speed of 900 revolutions per minute until the mixture is uniform to obtain the modified vegetable protein adhesive.
Example 4
The embodiment provides a modified isocyanate emulsion crosslinking agent, which is prepared from the following raw materials in parts by weight:
this example also provides a method for preparing the modified isocyanate emulsion crosslinking agent, comprising:
1. adding 4kg of gallic acid into 6kg of water heated to 60 ℃, and stirring for 5 minutes by adopting a mechanical stirring method until the gallic acid is uniformly mixed to obtain a gallic acid aqueous solution;
2. adding the prepared gallic acid aqueous solution into 20kg of pMDI to directly emulsify for 10 minutes to obtain the uniform modified isocyanate emulsion crosslinking agent.
The embodiment provides a modified vegetable protein adhesive, which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified vegetable protein adhesive, which comprises the following steps:
1. dispersing 30kg of protein meal in 70kg of water, and uniformly stirring at the rotating speed of 900 revolutions per minute to obtain a mixed solution containing the protein meal and the water;
2. adding 7kg of the modified isocyanate emulsion crosslinking agent into a mixed solution containing protein meal and water under the stirring condition of the rotating speed of 900 revolutions per minute, and stirring for 4 minutes for later use;
3. and (3) adding 8kg of curing agent into the system obtained in the step (2), and stirring for 14 minutes at the rotating speed of 900 revolutions per minute until the mixture is uniform to obtain the modified vegetable protein adhesive.
Comparative example 1 pMDI-only modified vegetable protein adhesive
The comparative example provides a modified vegetable protein adhesive, which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified vegetable protein adhesive, which comprises the following steps:
1. dispersing 30kg of protein meal in 70kg of water, and uniformly stirring at the rotating speed of 900 revolutions per minute to obtain a mixed solution containing the protein meal and the water;
2. adding 7kg of pMDI (unmodified) into a mixed solution containing protein meal and water under the stirring condition of the rotation speed of 900 revolutions per minute, and stirring for 5 minutes for later use;
3. and (3) adding 8kg of curing agent into the system obtained in the step (2), and stirring for 14 minutes under the condition of the rotation speed of 900 revolutions per minute until the curing agent is uniform to obtain the modified vegetable protein adhesive.
Examples of the experiments
The following test methods were used:
solid content test
1. Test materials modified vegetable protein adhesives prepared in examples 1-4 and comparative example 1.
2. The specific test method comprises the following steps:
taking a proper amount of prepared modified vegetable protein adhesive m1g, placing the adhesive in a tin foil paper box, and recording the total weight m of the adhesive and the tin foil paper box2g, then placing the adhesive in an oven at the temperature of 122 +/-2 ℃ to be dried to constant weight, and recording the total weight m of the cured adhesive and the tin foil carton3g, the calculation formula of the solid content of the adhesive is as follows. The above tests were carried out 3 times in parallelAnd taking an average value.
Adhesive solid content (W)1) The calculation formula is as follows:
W1(％)＝[m3-(m2-m1)]/m1×100％
prepressing formability test
Veneer: poplar with water content of 20-30% and thickness of 1.6 mm;
sizing: gluing the core plate with the glue amount of 270-325g/m2(double-sided);
cold pressing: the cold pressing pressure is 5-10MPa, and the cold pressing time is 30-60 min; (ii) a
Hot pressing: the hot pressing temperature is 120 ℃; the hot pressing pressure is 1.0-1.3 MPa; the hot pressing time is 10min (100s/min)
And (3) after cold pressing is finished according to the conditions, unloading and taking out the plate blank and standing for 30min, observing the condition that the periphery in the direction vertical to the wood fiber is rolled up to be degummed, measuring the side length without degummed, and expressing the pre-pressing forming performance of the glue by the ratio of the side length to the total side length (140 mm). The ratio is less than 40%, better between 40% and 60%, and better between 60% and better.
Water-resistant bond Strength test
The modified protein adhesives prepared in the embodiments 1-4 and the comparative example 1 of the invention are respectively utilized to manufacture three-layer plywood, and the following preparation process parameters are adopted:
veneer: poplar with water content of 20-30% and thickness of 1.6 mm;
sizing: gluing the core plate with the glue amount of 270-325g/m2(double-sided);
aging time: 30-90 min;
hot pressing: the hot pressing temperature is 120 ℃; the hot pressing pressure is 1.0-1.3 MPa; the hot pressing time is 10min (100s/min)
The three-layer plywood manufactured by the process is detected to have water-resistant bonding strength (class II) according to GB/T17657-2013 physical and chemical property experimental method for artificial boards and veneered artificial boards, and the result is shown in Table 1.
Table 1 main performance test results of adhesives and prepared plywood in examples 1 to 4 and comparative example 1
| Solid content (%) | Pre-press formability | Water-resistant bonding Strength (MPa) | |
| Comparative example 1 | 37.5 | Is difficult to form | 0.83 |
| Example 1 | 34.4 | Good taste | 1.31 |
| Example 2 | 34.8 | Good taste | 1.27 |
| Example 3 | 37.2 | Is preferably used | 1.34 |
| Example 4 | 37.6 | Good taste | 1.29 |
The results in table 1 show that the vegetable protein adhesive added with the isocyanate emulsion crosslinking agent prepared in examples 1-4 has better pre-pressing forming performance than the vegetable protein adhesive in comparative example 1, and the water-resistant bonding strength of the adhesive is also obviously enhanced, so that the requirements of type ii plywood are met.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A modified isocyanate crosslinking agent which is prepared by polymerizing a modifying agent and isocyanate; wherein the modifier contains a catechol group;
preferably, the modifier is a polyphenol substance, preferably a plant polyphenol, more preferably one or more selected from tannic acid, tannin, tea polyphenol and gallic acid; and/or the presence of a gas in the gas,
preferably, the isocyanate is selected from one or more of poly diphenylmethane diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, polyphenyl polymethylene polyisocyanate, TDI-tricyanomethylpropane adduct; and/or the presence of a gas in the gas,
preferably, the weight ratio of the modifier to isocyanate is (2-8):20, more preferably (3.5-5):20, even more preferably (4-5): 20; and/or the presence of a gas in the gas,
preferably, the modified isocyanate crosslinking agent is prepared by polymerizing a modifying agent and isocyanate in the presence of water; the weight ratio of water to isocyanate is preferably (5-15):20, more preferably (6-8): 20.
2. A modified isocyanate emulsion crosslinking agent is prepared from the following raw materials in parts by weight:
isocyanate 20 parts
5-15 parts of water
2-8 parts of a modifier;
preferably, the modified isocyanate emulsion crosslinking agent is prepared from the following raw materials in parts by weight:
isocyanate 20 parts
6-8 parts of water
3.5-5 parts of a modifier;
more preferably, the modified isocyanate emulsion crosslinking agent is prepared from the following raw materials in parts by weight:
isocyanate 20 parts
6-8 parts of water
4-5 parts of a modifier;
further preferably, the modifier is the same as the modifier of claim 1; and/or the isocyanate is the same as the isocyanate of claim 1.
3. A process for preparing a modified isocyanate crosslinking agent comprising polymerizing a modifying agent with an isocyanate; the polymerization is preferably carried out in the presence of water;
wherein the modifier is preferably the same as the modifier of claim 1; and/or the isocyanate is preferably the same as the isocyanate of claim 1.
4. A process for preparing a modified isocyanate emulsion crosslinker as claimed in claim 2 comprising:
1) providing an aqueous modifier solution;
2) mixing the aqueous modifier solution with isocyanate to polymerize the modifier with isocyanate; wherein, after the modifier aqueous solution is mixed with isocyanate in the step 2), the method preferably further comprises the step of emulsifying;
wherein the modifier is preferably the same as the modifier of claim 1; and/or the isocyanate is preferably the same as the isocyanate of claim 1.
5. A modified isocyanate emulsion crosslinker prepared by the process of claim 4.
6. Use of the modified isocyanate crosslinking agent of claim 1 or the modified isocyanate emulsion crosslinking agent of claim 2 or 5 for preparing a vegetable protein adhesive.
7. The modified vegetable protein adhesive is prepared from the following raw materials in parts by weight:
preferably, the modified vegetable protein adhesive is prepared from the following raw materials in parts by weight:
further preferably, the modified vegetable protein adhesive is prepared from the following raw materials in parts by weight:
preferably, the curing agent is glycidyl ether, and more preferably is one or more of polyamide polyamine epichlorohydrin resin, epoxy resin diluent glycerol triglycidyl ether and ethylene glycol diglycidyl ether.
8. The modified vegetable protein adhesive as claimed in claim 7, wherein,
the protein meal is plant protein meal; preferably, the protein meal is one or more of bean pulp, maple pulp, peanut meal, castor meal, cottonseed meal, rapeseed meal and alcohol lees; and/or the presence of a gas in the gas,
the granularity of the protein meal is 70-500 meshes, preferably 100-400 meshes, and more preferably 200-250 meshes; and/or the presence of a gas in the gas,
the protein meal is defatted protein meal; and/or the presence of a gas in the gas,
the protein content in the protein meal is more than 40 wt%, and preferably 40-60 wt%.
9. A method of preparing the modified protein adhesive of claim 7 or 8, comprising:
a) providing a mixed solution containing protein meal and water;
b) and mixing the mixed solution containing the protein meal and the water with the modified isocyanate emulsion crosslinking agent and the curing agent to prepare the modified vegetable protein adhesive.
10. Wood, bamboo, furniture, printed matter, building or finishing decoration containing the modified protein adhesive of claim 7 or 8.
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