CN103555256A - Modified water-based polyurethane adhesive - Google Patents
Modified water-based polyurethane adhesive Download PDFInfo
- Publication number
- CN103555256A CN103555256A CN201310483132.XA CN201310483132A CN103555256A CN 103555256 A CN103555256 A CN 103555256A CN 201310483132 A CN201310483132 A CN 201310483132A CN 103555256 A CN103555256 A CN 103555256A
- Authority
- CN
- China
- Prior art keywords
- diisocyanate
- aqueous polyurethane
- dioctyl phthalate
- tackiness agent
- modified aqueous
- 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.)
- Pending
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a modified water-based polyurethane adhesive which is prepared by mixing polyisocyanate, polyphenyl polyol phthalate with the molecular weight of 4000+/-2000g/mol, a foaming agent, a foam regulating additive, a catalyst, an antioxidant and organic bismuth, wherein the polyisocyanate is utilized so that the isocyanate groups in the mixture are more than the isocyanate reactive groups.
Description
Technical field
The present invention relates to single component, moisture-cure polyurethane adhesive (one-component, moisture-cure polyurethane adhesive), it can apply and solidify in room temperature, and forms permanent adhesive by the chemical reaction of the moisture with from substrate or environment (moisture).
Background technology
Polyurethane binder has good resistance to low temperature, water tolerance, oil-proofness and snappiness, has higher cohesive strength simultaneously, is widely used in the industries such as synthetic leather, laminated film, shoemaking.The performance of polyurethane binder depends on polyvalent alcohol that it is used and structure and the performance of isocyanic ester.Adopt the prepared polyurethane binder of polyether polyol to there is lower second-order transition temperature, snappiness and anti-hydrolytic performance, but its physical strength is low; The polyurethane binder that adopts polyester polyol to prepare has higher physical strength and oil-proofness, but its anti-hydrolytic performance is poor, and under low temperature, hardness is large, is difficult to meet market demands.Therefore, prepare polyurethane binder that a kind of low temperature softness and physical strength are high significant.Water-based polyurethane adhesive is usingd water as medium, have do not fire, nontoxic, non-environmental-pollution, the saving energy and the easy advantage such as processing.By the water-based polyurethane adhesive making from aggressiveness, because there is Coulomb's force and hydrogen bond action in its molecular chain, not only can make the aspects such as glueability and solvent borne polyurethane tackiness agent match in excellence or beauty, and can obtain multiple performance by modification.Lot of documents shows: polymerization occurs acrylate in polyaminoester emulsion, obtain the modified polyurethane emulsion of tool interpenetrating polymer networks structure, compare with unmodified polyaminoester emulsion, modified polyurethane emulsion particle increases, and thermostability, solvent resistance and mechanical property improve.Epoxy resin has the advantages such as modulus is high, intensity is high and chemical resistant properties is good, Heat stability is good, and can participate in the building-up reactions of aqueous polyurethane directly, improves water-fast, the solvent resistance of aqueous polyurethane and tensile strength etc.For this reason, take aqueous polyurethane as basis, dual modified with acrylate and epoxy resin, synthesized a kind of novel aqueous polyurethane adhesive, leather composite testing through a large amount of, obtains best leather complex condition, the demand of producing to meet elastic force leather.
Summary of the invention
The object of the present invention is to provide a kind of environment-friendly polyurethane adhesive, this tackiness agent is residual without organotin, and solvent residues is low, and ability to cure is strong, meets EU market standard.To achieve these goals, technical scheme of the present invention is as follows:
As one object of the present invention, a kind of modified aqueous polyurethane tackiness agent, is characterized in that, by following material is mixed and is obtained:
(1) polymeric polyisocyanate, the amount of polymeric polyisocyanate used is to make isocyanate groups that described mixture comprises more than isocyanate-reactive group;
(2) the polyphenyl dioctyl phthalate polyol ester that molecular weight is 4000 ± 2000g/mol;
(3) whipping agent: comprise Trimethylmethane, propane, normal butane, Trimethylmethane, pentane and pentamethylene; Methyl-isobutyl ether and dme; Dichloromonofluoromethane, fluoro trichloromethane, Freon 113; And/or partially halogenated hydrocarbon, trifluoromethane, 1, the mixture of a kind of or at least two kinds of whipping agents in the chloro-1-fluoroethane of 1-bis-, a chloro-tetrafluoroethane, chlorotrifluoroethane, chlorodifluoroethane, C2H4F2 C2H4F2, dichloro C2H4F2 C2H4F2, pentafluoride ethane, Tetrafluoroethane or dichloro one fluoroethane;
(4) foam regulates additive, comprises dimethyl siloxane that at 25 ℃, viscosity is 10-1000mPas or whiteruss, suds-stabilizing agent, saturated aliphatic hydrocarbon and silicone oil; The weight ratio of contained suds-stabilizing agent, silicone oil and whiteruss is 150 ± 50: 2 ± 1.2: 2 ± 1.2;
(5) catalyzer, comprise 2, 3-dimethyl-3, 4, 5, 6-tetrahydropyrimidine, three (dialkyl aminoalkyl)-s-Hexahydrotriazines are as three (N, N-dimethylaminopropyl)-s-Hexahydrotriazine, triethylamine, Tributylamine, dimethyl benzylamine, N-ethylmorpholine, N-methylmorpholine, positive cyclohexyl morpholine, dimethylcyclohexylamine, dimorpholine base Anaesthetie Ether, 2-(dimethylamino oxyethyl group) ethanol, 1, 4-diazabicyclo [2.2.2] octane, 1-azabicyclic [3.3.0] octane, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N, N ', N '-tetramethyl butane diamine, N, N, N ', N '-tetramethyl-hexane-1, 6-diamines, five methyl diethylentriamine, one or more in tetramethyl-diamino ethyl ether,
(6) oxidation inhibitor and organo-bismuth.
Further, described aliphatic diisocyanate is 1, hexamethylene-diisocyanate, 1,5-(2-methyl pentylidene) vulcabond, Isosorbide-5-Nitrae-(2-ethyl butylidene) vulcabond aliphatic diisocyanate, aromatic diisocyanate can be 1,5-naphthalene diisocyanate (1,5-NDI), 2,4-and 2,6-tolylene diisocyanate (TDI) and composition thereof.
Further, described polyphenyl dioctyl phthalate polyol ester is a kind of in polytrimethylene phthalate, polyphenyl dioctyl phthalate 1.3-butanediol ester, polyphenyl dioctyl phthalate 1.4-butanediol ester, polyphenyl dioctyl phthalate hexylene glycol ester and more than one.
Further, foam regulates additive to contain whiteruss, suds-stabilizing agent and silicone oil, and suds-stabilizing agent comprises polyalkylene glycol polysiloxane copolymer.
Further, described oxidation inhibitor is antioxidant 1010, and described organo-bismuth is organo-bismuth 8108.
As another object of the present invention, a kind of method of manufacturing described modified aqueous polyurethane tackiness agent, regulate additive, catalyzer to be placed in container with oxidation inhibitor together with organo-bismuth with higher molecular weight compound, whipping agent, the foam with isocyanate-reactive group aliphatic diisocyanate or aromatic diisocyanate, by described container sealing, and by above component homogenize, heat to 75-80 ℃, keep this temperature 15 minutes, mix.
Beneficial effect of the present invention: the present invention adopts methylcarbonate to replace traditional toluene, butanone, dimethyl formamide as thinner, can reach and optimize Compound Machining production environment, ensures that direct labor is healthy; With organo-bismuth, replace stannous octoate, product is residual without organotin; Adopt organic two rings and organic acid CAT S102 Catalyst catalyzer, greatly strengthened ability to cure, also improve stripping strength; The product that the present invention produces, safety, environmental protection all meet the existing ban of European Union, rules and regulations through the ITS of internal authority certification authority test result.
Embodiment
Embodiment 1
A kind of modified aqueous polyurethane tackiness agent, material by following parts by weight forms: 1, 320 parts of hexamethylene-diisocyanates, 120 parts of polytrimethylene phthalates, 20 parts of Trimethylmethanes, 5 parts of polyalkylene glycol polysiloxane copolymers, N, N, N ', 1.63 parts of N '-tetramethyl butane diamines, organo-bismuth 8108, 3.02 part, antioxidant 1010, 0.15 part, by 1, 320 parts of hexamethylene-diisocyanates, polytrimethylene phthalate and the higher molecular weight compound with isocyanate-reactive group, whipping agent, foam regulates additive, catalyzer is placed in container together with organo-bismuth with oxidation inhibitor, by described container sealing, and by above component homogenize, heat to 75-80 ℃, keep this temperature 15 minutes, mix.
Embodiment 2
A tackiness agent, is comprised of the material of following parts by weight: and l,5 naphthylene diisocyanate (1,5-NDI), 260 parts, 2,4-and 2,6-tolylene diisocyanate (TDI) mixture, 180 parts, polyphenyl dioctyl phthalate 1.3-butanediol ester and polyphenyl dioctyl phthalate 1.4-butanediol ester mixture, 40 parts of dichloro C2H4F2 C2H4F2s, 4 parts of dimethyl siloxanes, 0.6 part of Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane, 8108,2.02 parts of organo-bismuths, antioxidant 1010,0.25 part, wherein 1, 5-naphthalene diisocyanate (1,5-NDI), 2, 4-and 2, the mass ratio of 6-tolylene diisocyanate (TDI) is 1:3, will: l,5 naphthylene diisocyanate (1, 5-NDI), 260 parts, 2,4-and 2,6-tolylene diisocyanate (TDI) mixture, 180 parts, polyphenyl dioctyl phthalate 1.3-butanediol ester and polyphenyl dioctyl phthalate 1.4-butanediol ester mixture, 40 parts of dichloro C2H4F2 C2H4F2s, 4 parts of dimethyl siloxanes, 0.6 part of Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane, 8108,2.02 parts of organo-bismuths, antioxidant 1010,0.25 part is placed in container, by described container sealing, and by above component homogenize, heats to 75-80 ℃, keeps this temperature 15 minutes, mixes.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (6)
1. a modified aqueous polyurethane tackiness agent, is characterized in that, by following material is mixed and is obtained:
(1) polymeric polyisocyanate, the amount of polymeric polyisocyanate used is to make isocyanate groups that described mixture comprises more than isocyanate-reactive group;
(2) the polyphenyl dioctyl phthalate polyol ester that molecular weight is 4000 ± 2000g/mol;
(3) whipping agent: comprise Trimethylmethane, propane, normal butane, Trimethylmethane, pentane and pentamethylene; Methyl-isobutyl ether and dme; Dichloromonofluoromethane, fluoro trichloromethane, Freon 113; And/or partially halogenated hydrocarbon, trifluoromethane, 1, the mixture of a kind of or at least two kinds of whipping agents in the chloro-1-fluoroethane of 1-bis-, a chloro-tetrafluoroethane, chlorotrifluoroethane, chlorodifluoroethane, C2H4F2 C2H4F2, dichloro C2H4F2 C2H4F2, pentafluoride ethane, Tetrafluoroethane or dichloro one fluoroethane;
(4) foam regulates additive, comprises dimethyl siloxane that at 25 ℃, viscosity is 10-1000mPas or whiteruss, suds-stabilizing agent, saturated aliphatic hydrocarbon and silicone oil; The weight ratio of contained suds-stabilizing agent, silicone oil and whiteruss is 150 ± 50: 2 ± 1.2: 2 ± 1.2;
(5) catalyzer, comprise 2, 3-dimethyl-3, 4, 5, 6-tetrahydropyrimidine, three (dialkyl aminoalkyl)-s-Hexahydrotriazines are as three (N, N-dimethylaminopropyl)-s-Hexahydrotriazine, triethylamine, Tributylamine, dimethyl benzylamine, N-ethylmorpholine, N-methylmorpholine, positive cyclohexyl morpholine, dimethylcyclohexylamine, dimorpholine base Anaesthetie Ether, 2-(dimethylamino oxyethyl group) ethanol, 1, 4-diazabicyclo [2.2.2] octane, 1-azabicyclic [3.3.0] octane, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N, N ', N '-tetramethyl butane diamine, N, N, N ', N '-tetramethyl-hexane-1, 6-diamines, five methyl diethylentriamine, one or more in tetramethyl-diamino ethyl ether,
(6) oxidation inhibitor and organo-bismuth.
2. modified aqueous polyurethane tackiness agent according to claim 1, it is characterized in that, aliphatic diisocyanate is hexamethylene diisocyanate, 1,5-(2-methyl pentylidene) vulcabond, 1,4-(2-ethyl butylidene) vulcabond aliphatic diisocyanate, aromatic diisocyanate comprises l,5 naphthylene diisocyanate (1,5-NDI), 2,4-and 2,6-tolylene diisocyanate (TDI) and composition thereof.
3. modified aqueous polyurethane tackiness agent according to claim 1, it is characterized in that, described polyphenyl dioctyl phthalate polyol ester is a kind of in polytrimethylene phthalate, polyphenyl dioctyl phthalate 1.3-butanediol ester, polyphenyl dioctyl phthalate 1.4-butanediol ester, polyphenyl dioctyl phthalate hexylene glycol ester and more than one.
4. modified aqueous polyurethane tackiness agent according to claim 1, is characterized in that, foam regulates additive to contain whiteruss, suds-stabilizing agent and silicone oil, and suds-stabilizing agent comprises polyalkylene glycol polysiloxane copolymer.
5. modified aqueous polyurethane tackiness agent according to claim 1, is characterized in that, described oxidation inhibitor is antioxidant 1010, and described organo-bismuth is organo-bismuth 8108.
6. a method of manufacturing modified aqueous polyurethane tackiness agent as claimed in claim 1, regulate additive, catalyzer to be placed in container with oxidation inhibitor together with organo-bismuth with whipping agent, foam aliphatic diisocyanate or aromatic diisocyanate, by described container sealing, and by above component homogenize, heat to 75-80 ℃, keep this temperature 15 minutes, mix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310483132.XA CN103555256A (en) | 2013-10-16 | 2013-10-16 | Modified water-based polyurethane adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310483132.XA CN103555256A (en) | 2013-10-16 | 2013-10-16 | Modified water-based polyurethane adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103555256A true CN103555256A (en) | 2014-02-05 |
Family
ID=50009630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310483132.XA Pending CN103555256A (en) | 2013-10-16 | 2013-10-16 | Modified water-based polyurethane adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103555256A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101883805A (en) * | 2007-12-03 | 2010-11-10 | 巴斯夫欧洲公司 | Single-component polyurethane adhesive |
| CN102732206A (en) * | 2012-07-04 | 2012-10-17 | 浙江多邦化工有限公司 | Environment-friendly polyurethane binder |
-
2013
- 2013-10-16 CN CN201310483132.XA patent/CN103555256A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101883805A (en) * | 2007-12-03 | 2010-11-10 | 巴斯夫欧洲公司 | Single-component polyurethane adhesive |
| CN102732206A (en) * | 2012-07-04 | 2012-10-17 | 浙江多邦化工有限公司 | Environment-friendly polyurethane binder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Du et al. | Synthesis and characterization of waterborne polyurethane adhesive from MDI and HDI | |
| CN101787253B (en) | One-component solvent-free polyurethane adhesive and preparation method thereof and raw material composition | |
| US10947336B2 (en) | Moisture curable hot melt urethane composition, method for producing cured foam of same, synthetic leather and method for producing synthetic leather | |
| Khoon Poh et al. | Polyurethane wood adhesive from palm oil-based polyester polyol | |
| CN103820069A (en) | Double-component solvent-free polyurethane adhesive and preparation method thereof | |
| CN107118734A (en) | A kind of double component solvent-free polyurethane adhesive | |
| RU2010127150A (en) | ONE-COMPONENT POLYURETHANE ADHESIVE | |
| CN103597050A (en) | Impact-modified adhesives | |
| CN106674475B (en) | A kind of polyurethane aqueous material, preparation method and its application | |
| CN103215006A (en) | Low viscosity solvent-free polyurethane laminating adhesive and preparation method thereof | |
| CN102827340A (en) | Organosilicon-modified waterborne polyurethane composite material and applications thereof | |
| CA2874970A1 (en) | A composition in the form of a dispersion comprising a lignin, a method for the manufacturing thereof and use thereof | |
| EP3347391A1 (en) | Blocked polyurethane tougheners for epoxy adhesives | |
| CN107556962B (en) | Two-component polyurethane adhesive for building and preparation method thereof | |
| CN105969293A (en) | Two-component solvent-free plant oil-based adhesive | |
| CN102775579B (en) | Preparation method of polyurethane foam with water sealing performance | |
| CN106750095A (en) | Polyurethane adhesive combined polyether, polyurethane adhesive and preparation method thereof | |
| CN109206569A (en) | A kind of aqueous polyurethane and Aqueous Polyurethane Adhesives and preparation method thereof | |
| CN102516920A (en) | Aqueous polyurethane adhesive and preparation method thereof | |
| CN102666755A (en) | Coating material for hand application | |
| CN112175570A (en) | Polyurethane adhesive and preparation method thereof | |
| US20150252231A1 (en) | Latent-reactive hot-melt adhesive composition | |
| CN106750119B (en) | A kind of combined polyether, polyurethane adhesive feedstock composition and its application | |
| CN104178077A (en) | Polyurethane adhesive used for durable and environmentally friendly plastic runway | |
| JP7104967B2 (en) | Surface treatment agent and bonding method using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140205 |