CN109988537A - 一种淀粉改性聚氨酯胶黏剂及其制备方法 - Google Patents
一种淀粉改性聚氨酯胶黏剂及其制备方法 Download PDFInfo
- Publication number
- CN109988537A CN109988537A CN201910350358.XA CN201910350358A CN109988537A CN 109988537 A CN109988537 A CN 109988537A CN 201910350358 A CN201910350358 A CN 201910350358A CN 109988537 A CN109988537 A CN 109988537A
- Authority
- CN
- China
- Prior art keywords
- parts
- starch
- starch conversion
- polyurethane
- adhesive
- 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.)
- Granted
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 47
- 239000000853 adhesive Substances 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 42
- 229920002472 Starch Polymers 0.000 title claims abstract description 34
- 239000008107 starch Substances 0.000 title claims abstract description 34
- 235000019698 starch Nutrition 0.000 title claims abstract description 33
- 239000004814 polyurethane Substances 0.000 title claims abstract description 26
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920000570 polyether Polymers 0.000 claims abstract description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 9
- 150000003384 small molecules Chemical group 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 3
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 3
- 230000018044 dehydration Effects 0.000 claims description 16
- 238000006297 dehydration reaction Methods 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 208000005156 Dehydration Diseases 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 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 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- IFVTZJHWGZSXFD-UHFFFAOYSA-N biphenylene Chemical group C1=CC=C2C3=CC=CC=C3C2=C1 IFVTZJHWGZSXFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 125000005586 carbonic acid group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000001802 infusion Methods 0.000 claims 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims 1
- -1 phenylenedimethylidyne Chemical group 0.000 claims 1
- 235000012222 talc Nutrition 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 229920002261 Corn starch Polymers 0.000 abstract description 17
- 235000019759 Maize starch Nutrition 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000004135 Bone phosphate Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 150000002334 glycols Chemical class 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 235000019482 Palm oil Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008120 corn starch Substances 0.000 description 3
- 229940099112 cornstarch Drugs 0.000 description 3
- 239000002540 palm oil Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical group OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KPTLPIAOSCGETM-UHFFFAOYSA-N benzene 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O.c1ccccc1 KPTLPIAOSCGETM-UHFFFAOYSA-N 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种淀粉改性聚氨酯胶黏剂及其制备方法，涉及胶粘剂产品制备技术领域，由如下重量份数的原料制成：二异氰酸酯30‑60份、聚醚多元醇100‑400份、淀粉100‑600份、小分子扩链剂2‑10份、消泡剂1‑5份、催化剂2‑10份、填充剂100‑500份、环保增塑剂100‑300份、有机溶剂10‑40份；本发明使用组合型的聚醚多元醇与填充剂、氧化玉米淀粉混合均匀，再缓慢滴加异氰酸酯，控制反应温度不超过90℃，再加入小分子扩链剂，反应合成带有填充物的淀粉改性聚氨酯的预聚体大分子，最后加入催化剂、消泡剂和有机溶剂。
Description
技术领域：
本发明涉及胶粘剂产品制备技术领域，具体涉及一种淀粉改性聚氨酯胶黏剂及其制备方法。
背景技术：
根据有关资料显示，2006-2015年，我国人造板工业用胶黏剂消耗量年平均增长率为10.1％。2015年我国木材胶黏剂87.8％用于人造板工业，主要品种为脲醛树脂胶(含改性)和酚醛树脂胶。脲醛树脂胶(含改性)消耗量约为1392万t，占人造板工业胶黏剂用量近91％。酚醛树脂胶消耗量约为138万t，约占人造板工业胶黏剂用量的9％。
聚氨酯胶粘剂是指在分子链中含有氨基甲酸酯基团(－NHCOO－)的高分子材料，具有优异的性能。聚氨酯胶黏剂已经成为继脲醛树脂(UF)、酚醛树脂(PF)、三聚氰胺-甲醛树脂(MF)和聚醋酸乙烯乳液(PVAc)之后的又一重要木材工业用胶黏剂。
聚氨酯胶黏剂与木材的水分和羟基反应，固化交联而形成稳定的化学结构。该类型胶黏剂具有力学强度高、绝缘、耐热、耐水、耐腐蚀性高、用于木材工业中使得产品具有尺寸稳定性好、不含甲醛等优点。目前由于价格昂贵，主要用于高端板材加工领域。目前行业开发者正通过引入价格较低的改性材料来降低材料成本，使聚氨酯胶黏剂成本降低而获得更快的推广使用。
淀粉胶粘剂是近年来采用较多的一种瓦楞纸箱生产用胶粘剂，主要原料是玉米淀粉或木薯淀粉。由于生产淀粉胶粘剂原料来源广、价格低、粘接性能较好，因此推广使用较快。
由于原淀粉中含有羟基，通过在聚氨酯预聚阶段引入原淀粉，淀粉中的羟基与异氰酸根进行接枝共聚反应，淀粉易于获得且成本较低，可制备得到一种聚氨酯-淀粉胶黏剂。该胶黏剂成本较低，且同时具备了聚氨酯高强度、高粘结性能的特点，可以应用于木材胶黏剂领域，以替代传统的“三醛”胶黏剂。
发明内容：
本发明所要解决的技术问题在于提供一种淀粉改性聚氨酯胶黏剂，利用淀粉所含羟基与-NCO发生接枝反应来对聚氨酯进行改性，显著改善所制胶黏剂的使用性能。
本发明所要解决的技术问题采用以下的技术方案来实现：
一种淀粉改性聚氨酯胶黏剂，由如下重量份数的原料制成：
二异氰酸酯30-60份、聚醚多元醇100-400份、淀粉100-600份、小分子扩链剂2-10份、消泡剂1-5份、催化剂2-10份、填充剂100-500份、环保增塑剂100-300份、有机溶剂10-40份。
所述二异氰酸酯选自异佛尔酮二异氰酸酯IPDI、二苯基甲烷二异氰酸酯MDI、1,6-己二异氰酸酯HDI、苯二亚甲基二异氰酸酯XDI、萘-1,5-二异氰酸酯NDI中的一种或两种。
所述聚醚多元醇选自官能度为2～4、数均分子量为1000～5000的聚醚多元醇中的两种。
所述淀粉为氧化玉米淀粉。
所述小分子扩链剂选自新戊二醇、三羟甲基丙烷、二羟甲基丙酸中的一种。
所述消泡剂为聚醚改性硅氧烷共聚合物。
所述催化剂选自有机金属化合物类催化剂，优选辛酸亚锡或二月桂酸二丁基锡。
所述填充剂选自滑石粉、高岭土、碳酸钙、白炭黑中的一种或几种。
所述环保增塑剂选自长链氯化石蜡、氯代棕榈油甲酯、环氧大豆油中的一种或两种。
所述有机溶剂选自碳酸二甲酯、丙酮中的一种。
上述淀粉改性聚氨酯胶黏剂的制备方法，包括以下步骤：
向反应釜中依次加入聚醚多元醇、淀粉、填充剂和环保增塑剂，边搅拌边升温至100-110℃真空脱水，真空度控制在0.07-0.09MPa；脱水结束后降温至70-80℃，并缓慢加入二异氰酸酯，控制温度不超过90℃，滴加完毕后保温反应；再加入小分子扩链剂保温反应；然后加入催化剂和消泡剂，最后加入有机溶剂，搅拌均匀，继续降温至50-60℃，出料，密封保存。
本发明的有益效果是：
(1)本发明使用组合型的聚醚多元醇与填充剂、氧化玉米淀粉混合均匀，再缓慢滴加异氰酸酯，控制反应温度不超过90℃，再加入小分子扩链剂，反应合成带有填充物的淀粉改性聚氨酯的预聚体大分子，最后加入催化剂、消泡剂和有机溶剂，催化剂可以加快胶黏剂在使用时的固化速度，消泡剂可以消除固化成膜时的气泡，有机溶剂适当降低体系粘度，同时设计使体系的-NCO/-OH摩尔比为1.3-2.5。
(2)氧化玉米淀粉的结构中含有羟基、羰基和羧基，羟基可与-NCO接枝反应，羧基可提升与基材的附着力，同时氧化玉米淀粉的加入极大降低了聚氨酯胶黏剂的制备成本。
具体实施方式：
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例，进一步阐述本发明。
实施例1
配料表如下：
向反应釜中依次加入聚醚二元醇2000、聚醚三元醇3000、氧化玉米淀粉、滑石粉和长链氯化石蜡，边搅拌边升温至110℃真空脱水，真空脱水2h，真空度控制在0.08MPa；脱水结束后降温至80℃，并缓慢加入二异氰酸酯MDI，时间控制在2h，控制温度不超过90℃，滴加完毕后保温反应3h；再加入新戊二醇保温反应3h；然后加入二月桂酸二丁基锡和聚醚改性硅氧烷共聚合物，最后加入丙酮，搅拌均匀，继续降温至50℃，出料，密封保存。
实施例2
配料表如下：
| 原料 | 用量/g |
| 聚醚三元醇3000 | 120 |
| 聚醚二元醇4000 | 80 |
| 氯代棕榈油甲酯 | 140 |
| 重质碳酸钙 | 200 |
| 氧化玉米淀粉 | 300 |
| 二异氰酸酯MDI | 48 |
| 二羟甲基丙酸 | 2 |
| 二月桂酸二丁基锡 | 1 |
| 聚醚改性硅氧烷共聚合物 | 1 |
| 碳酸二甲酯 | 15 |
向反应釜中依次加入聚醚三元醇3000、聚醚二元醇4000、氧化玉米淀粉、重质碳酸钙和氯代棕榈油甲酯，边搅拌边升温至110℃真空脱水，真空脱水2h，真空度控制在0.08MPa；脱水结束后降温至80℃，并缓慢加入二异氰酸酯MDI，时间控制在2h，控制温度不超过90℃，滴加完毕后保温反应3h；再加入二羟甲基丙酸保温反应3h；然后加入二月桂酸二丁基锡和聚醚改性硅氧烷共聚合物，最后加入碳酸二甲酯，搅拌均匀，继续降温至50℃，出料，密封保存。
实施例3
配料表如下：
| 原料 | 用量/g |
| 聚醚三元醇5000 | 100 |
| 聚醚二元醇4000 | 120 |
| 环氧大豆油 | 180 |
| 高岭土 | 150 |
| 氧化玉米淀粉 | 350 |
| 二异氰酸酯IPDI | 42 |
| 二羟甲基丙酸 | 4 |
| 二月桂酸二丁基锡 | 3 |
| 聚醚改性硅氧烷共聚合物 | 2 |
| 碳酸二甲酯 | 20 |
向反应釜中依次加入聚醚三元醇5000、聚醚二元醇4000、氧化玉米淀粉、高岭土和环氧大豆油，边搅拌边升温至110℃真空脱水，真空脱水2h，真空度控制在0.08MPa；脱水结束后降温至80℃，并缓慢加入二异氰酸酯IPDI，时间控制在2h，控制温度不超过90℃，滴加完毕后保温反应3h；再加入二羟甲基丙酸保温反应3h；然后加入二月桂酸二丁基锡和聚醚改性硅氧烷共聚合物，最后加入碳酸二甲酯，搅拌均匀，继续降温至50℃，出料，密封保存。
实施例4
配料表如下：
向反应釜中依次加入聚醚三元醇5000、聚醚三元醇3000、氧化玉米淀粉、重质碳酸钙和长链氯化石蜡，边搅拌边升温至110℃真空脱水，真空脱水2h，真空度控制在0.08MPa；脱水结束后降温至80℃，并缓慢加入二异氰酸酯IPDI，时间控制在2h，控制温度不超过90℃，滴加完毕后保温反应3h；再加入三羟基丙烷保温反应3h；然后加入二月桂酸二丁基锡和聚醚改性硅氧烷共聚合物，最后加入碳酸二甲酯，搅拌均匀，继续降温至50℃，出料，密封保存。
对照例1
以实施例4为对照，设置以等量玉米淀粉替代氧化玉米淀粉的对照例1，其余操作完全相同。
对照例2
以实施例4为对照，设置不添加氧化玉米淀粉的对照例2，其余操作完全相同。
对照例3
以实施例4为对照，设置不添加催化剂的对照例3，其余操作完全相同。
分别利用实施例1-4、对照例1-3制备胶黏剂，对照例3因不加催化剂，所制胶黏剂在室温下固化十分缓慢，24h后仍未固化，因此不评价其使用性能。
依照国标GB/T 17657-2013制作胶合板试件并测定胶合强度，测定结果如表1所示。
表1所制胶黏剂的胶合性能
由表1可知，通过氧化玉米淀粉的添加能够显著增强所制胶黏剂的胶合性能，并且常规玉米淀粉的增强效果远不如氧化玉米淀粉，同时实施例1-4所制胶黏剂对木材的胶合性能明显优于目前现有胶黏剂。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (10)
1.一种淀粉改性聚氨酯胶黏剂，其特征在于：由如下重量份数的原料制成：
二异氰酸酯30-60份、聚醚多元醇100-400份、淀粉100-600份、小分子扩链剂2-10份、消泡剂1-5份、催化剂2-10份、填充剂100-500份、环保增塑剂100-300份、有机溶剂10-40份。
2.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述二异氰酸酯选自异佛尔酮二异氰酸酯IPDI、二苯基甲烷二异氰酸酯MDI、1,6-己二异氰酸酯HDI、苯二亚甲基二异氰酸酯XDI、萘-1,5-二异氰酸酯NDI中的一种或两种；所述聚醚多元醇选自官能度为2～4、数均分子量为1000～5000的聚醚多元醇中的两种。
3.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述淀粉为氧化玉米淀粉。
4.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述小分子扩链剂选自新戊二醇、三羟甲基丙烷、二羟甲基丙酸中的一种。
5.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述消泡剂为聚醚改性硅氧烷共聚合物。
6.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述催化剂选自有机金属化合物类催化剂。
7.根据权利要求6所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述催化剂优选辛酸亚锡或二月桂酸二丁基锡。
8.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述填充剂选自滑石粉、高岭土、碳酸钙、白炭黑中的一种或几种；所述环保增塑剂选自长链氯化石蜡、氯代棕榈油甲酯、环氧大豆油中的一种或两种。
9.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述有机溶剂选自碳酸二甲酯、丙酮中的一种。
10.如权利要求1所述的淀粉改性聚氨酯胶黏剂的制备方法，其特征在于：包括以下步骤：
向反应釜中依次加入聚醚多元醇、淀粉、填充剂和环保增塑剂，边搅拌边升温至100-110℃真空脱水，真空度控制在0.07-0.09MPa；脱水结束后降温至70-80℃，并缓慢加入二异氰酸酯，控制温度不超过90℃，滴加完毕后保温反应；再加入小分子扩链剂保温反应；然后加入催化剂和消泡剂，最后加入有机溶剂，搅拌均匀，继续降温至50-60℃，出料，密封保存。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910350358.XA CN109988537B (zh) | 2019-04-28 | 2019-04-28 | 一种淀粉改性聚氨酯胶黏剂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910350358.XA CN109988537B (zh) | 2019-04-28 | 2019-04-28 | 一种淀粉改性聚氨酯胶黏剂及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109988537A true CN109988537A (zh) | 2019-07-09 |
| CN109988537B CN109988537B (zh) | 2021-07-23 |
Family
ID=67135393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910350358.XA Active CN109988537B (zh) | 2019-04-28 | 2019-04-28 | 一种淀粉改性聚氨酯胶黏剂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109988537B (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724447A (zh) * | 2019-10-12 | 2020-01-24 | 海南必凯水性新材料有限公司 | 一种水性数码印刷底胶及其制备方法 |
| CN112831309A (zh) * | 2021-03-11 | 2021-05-25 | 安徽扬子地板股份有限公司 | 一种墙体无机板用胶黏剂及其制备方法 |
| CN114907806A (zh) * | 2022-03-30 | 2022-08-16 | 上海中南建筑材料有限公司 | 一种人造板材用植本胶粘剂及其制备方法 |
| CN116676058A (zh) * | 2023-07-03 | 2023-09-01 | 广东晋泽科技有限公司 | 一种高强度高韧性淀粉胶黏剂和制备工艺 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156840A (en) * | 1998-01-26 | 2000-12-05 | Kuraray Co., Ltd. | Method for producing aqueous emulsion of polyurethane |
| CN101314235A (zh) * | 2008-06-16 | 2008-12-03 | 北华大学 | 水性高分子-异氰酸酯秸秆人造板及其制备方法 |
| CN102153985A (zh) * | 2011-02-26 | 2011-08-17 | 浙江万和高分子材料有限公司 | 植物原料改性聚氨酯热熔胶及其生产工艺 |
| CN106010409A (zh) * | 2016-06-28 | 2016-10-12 | 广西众昌树脂有限公司 | 木材用聚氨酯热熔胶 |
| CN106118575A (zh) * | 2016-06-28 | 2016-11-16 | 广西众昌树脂有限公司 | 湿固化聚氨酯热熔胶的制备方法 |
| CN109021860A (zh) * | 2018-06-02 | 2018-12-18 | 安徽扬帆充气游乐设备制造有限公司 | 一种环境耐水型充气艇用胶黏剂 |
-
2019
- 2019-04-28 CN CN201910350358.XA patent/CN109988537B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156840A (en) * | 1998-01-26 | 2000-12-05 | Kuraray Co., Ltd. | Method for producing aqueous emulsion of polyurethane |
| CN101314235A (zh) * | 2008-06-16 | 2008-12-03 | 北华大学 | 水性高分子-异氰酸酯秸秆人造板及其制备方法 |
| CN102153985A (zh) * | 2011-02-26 | 2011-08-17 | 浙江万和高分子材料有限公司 | 植物原料改性聚氨酯热熔胶及其生产工艺 |
| CN106010409A (zh) * | 2016-06-28 | 2016-10-12 | 广西众昌树脂有限公司 | 木材用聚氨酯热熔胶 |
| CN106118575A (zh) * | 2016-06-28 | 2016-11-16 | 广西众昌树脂有限公司 | 湿固化聚氨酯热熔胶的制备方法 |
| CN109021860A (zh) * | 2018-06-02 | 2018-12-18 | 安徽扬帆充气游乐设备制造有限公司 | 一种环境耐水型充气艇用胶黏剂 |
Non-Patent Citations (1)
| Title |
|---|
| 韩利等: "可再生原料为交联剂制备水性聚氨酯脲 ", 《广州化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724447A (zh) * | 2019-10-12 | 2020-01-24 | 海南必凯水性新材料有限公司 | 一种水性数码印刷底胶及其制备方法 |
| CN112831309A (zh) * | 2021-03-11 | 2021-05-25 | 安徽扬子地板股份有限公司 | 一种墙体无机板用胶黏剂及其制备方法 |
| CN114907806A (zh) * | 2022-03-30 | 2022-08-16 | 上海中南建筑材料有限公司 | 一种人造板材用植本胶粘剂及其制备方法 |
| CN116676058A (zh) * | 2023-07-03 | 2023-09-01 | 广东晋泽科技有限公司 | 一种高强度高韧性淀粉胶黏剂和制备工艺 |
| CN116676058B (zh) * | 2023-07-03 | 2023-12-22 | 广东晋泽科技有限公司 | 一种高强度高韧性淀粉胶黏剂和制备工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109988537B (zh) | 2021-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109988537A (zh) | 一种淀粉改性聚氨酯胶黏剂及其制备方法 | |
| Moubarik et al. | Cornstarch and tannin in phenol–formaldehyde resins for plywood production | |
| CN109181612B (zh) | 一种耐水性生物基胶黏剂及其制备方法 | |
| CN101921381B (zh) | 应用于水基真空吸塑胶用胶黏剂的聚氨酯乳液的制备方法 | |
| CN110003398B (zh) | 一种聚乙烯醇改性水性聚氨酯-丙烯酸酯乳液 | |
| CN112300734B (zh) | 一种无醛胶合板用胶黏剂及其制备方法和使用其制备的胶合板 | |
| CN103833956A (zh) | 一种大分子量聚氨酯丙烯酸酯树脂及其制备方法 | |
| CN110194930B (zh) | 一种耐高温抗高寒涂料及其应用 | |
| CN101824294A (zh) | 四元共聚水性聚氨酯汽车内饰胶的制备方法 | |
| US8324299B2 (en) | Moisture-curable hot melt adhesive | |
| JP2002226820A (ja) | リグノセルロース系熱圧成形体用接着剤組成物、及びそれを用いた熱圧成形体の製造方法 | |
| CN101402716A (zh) | 一种固化剂二苯基甲烷二异氰酸酯及1,6-己二异氰酸酯混合预聚物及其制备方法 | |
| CN114085353B (zh) | 一种光-热双重固化树脂及其制备方法 | |
| CN104292419B (zh) | 一种高性能绿色环保家具涂料用双组分聚氨酯改性不饱和聚酯的制备方法 | |
| CN108164678A (zh) | 一种可uv固化的大豆油基水性聚氨酯及其制备方法 | |
| Li et al. | A sustainable tannin-citric acid wood adhesive with favorable bonding properties and water resistance | |
| Chen et al. | Optimized condition for eco-friendly wood composites manufactured from castor oil-based polyurethane | |
| KR20140119141A (ko) | 목재 접착제 배합물 | |
| CN101921387B (zh) | 一种木质素改性pet复合材料及其制备方法 | |
| EP2877513B1 (en) | Uv-curing hot melt adhesive containing low content of oligomers | |
| CN111171277A (zh) | 聚氨酯弹***联剂及高强韧植物蛋白胶黏剂与应用 | |
| CN103030767A (zh) | 可降解的辐射固化聚氨酯丙烯酸酯低聚物及其制备方法 | |
| CN103923523A (zh) | 一种多臂星形丙烯酸酯共聚物改性的聚氨酯油墨及其制备方法 | |
| CN111116857B (zh) | 一种乙烯基树脂及其制备方法 | |
| CN110003416B (zh) | 一种可乳化异氰酸酯及其制备方法及其乳化方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A starch modified polyurethane adhesive and its preparation method Effective date of registration: 20230630 Granted publication date: 20210723 Pledgee: Lu'an Yeji Sub branch of Agricultural Bank of China Co.,Ltd. Pledgor: ANHUI JIANGXING LIANCHUANG NEW MATERIALS TECHNOLOGY CO.,LTD. Registration number: Y2023980046766 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| CP03 | Change of name, title or address |
Address after: 237000 Industrial Avenue, Yaoli Town, Yeji District, Lu'an City, Anhui Province Patentee after: Anhui Jiangxing Lianchuang New Materials Technology Co.,Ltd. Country or region after: China Address before: 237000 Weisan Road, Yeji District, Lu'an City, Anhui Province Patentee before: ANHUI JIANGXING LIANCHUANG NEW MATERIALS TECHNOLOGY CO.,LTD. Country or region before: China |