CN1048517C - Method for preparing single component polyurethane adhesive/seal gum - Google Patents
Method for preparing single component polyurethane adhesive/seal gum Download PDFInfo
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- CN1048517C CN1048517C CN97100755A CN97100755A CN1048517C CN 1048517 C CN1048517 C CN 1048517C CN 97100755 A CN97100755 A CN 97100755A CN 97100755 A CN97100755 A CN 97100755A CN 1048517 C CN1048517 C CN 1048517C
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Abstract
The present invention belongs to a preparation method for single-component polyurethane adhesive/sealing gum, which is characterized in that home-made tertiary hydroxy polyether (M is 5000) and aromatic diisocyanate are additionally polymerized, dihydroxy alcohol containing 3 or 4 carbon atoms is used for chain extending and grafting, and a catalyst, a block agent and an anhydrous filler are added. The preparation method realizes that the preparation method substitutes for the existing single-component polyurethane adhesive/sealing gum product. When a product is prepared, a material with low molecular weight is used for substituting for polyether with high molecular weight. The main conditions of the preparation method comprise evacuation, dehydration, nitrogen protection and suitable temperature. The present invention has the advantages of simple and convenient preparation technology, easy raw material obtainment and low price.
Description
The invention belongs to a preparation method of a polyurethane adhesive, and particularly relates to a preparation method of a single-component polyurethane adhesive/sealant.
At present, the single-component polyurethane adhesive/sealant is mainly applied to bonding and sealing between windshields and car bodies of medium and high-grade cars, so that the overall rigidity and the sealing performance of the cars are good. The bonding process is used for the windshields in the production of saloon cars in developed countries, the bonding process is also used for most windshields introduced into cars in China, but the single-component polyurethane adhesive/sealant used for bonding the windshields is imported all the time. Only a few developed countries in the world, such as ESSEX, Inc. in the United states, EMS-TOGO, Switzerland, are able to produce high quality products of this kind. They must use high molecular weight (M8000) polyethers in the preparation of such polyurethane adhesives/sealants, and are expensive to obtain with high technology.
The purpose of the invention is: the method comprises the steps of using domestic ternary hydroxyl-terminated polyether with the molecular weight of 4790-5500 to replace imported polyether with the average molecular weight of 8000 to react with excessive aromatic diisocyanate, using binary low-molecular-weight alcohol containing three or four carbon atoms to carry out chain extension and grafting, and adding a catalyst, a filler and a solvent to obtain the single-component polyurethane adhesive/sealant, so that the problem that the single-component polyurethane adhesive/sealant cannot be produced by using low-molecular-weight polyether is solved.
The technical scheme of the invention is as follows: taking corresponding amount of ternary hydroxyl-terminated polyether (with average molecular weight of 5000) and excessive aromatic diisocyanate to carry out polyaddition reaction according to the following formula, then carrying out chain extension and grafting by using three-carbon or four-carbon binary low molecular alcohol, wherein the molar ratio of hydroxyl to isocyanate is 1: 1.5-2.4, adding a catalyst to complete the reaction, and then adding a blocking agent and a filler to prepare the single-component polyurethane adhesive/sealant. The use formula and the raw materials are as follows:
raw material weight portion
Domestic hydroxyl-terminated ternary polyether 35-45 with molecular weight of 4790-5500
4 to 7.5 of aromatic diisocyanate
0.02-0.5% of three-carbon or four-carbon dihydric alcohol
15-26% of filler
Solvent(s)
When using the drying material, 3-5
25-35% by weight of a moisture-containing filler
0.02-0.50% of catalyst
0.1 to 0.6 of a blocking agent
8-20% of plasticizer
Description of the raw materials used:
1. the molecular weight of the domestic hydroxyl-terminated ternary polyether is 4790-5500.
2. The aromatic diisocyanates are mainly MDI, TDI and NDI (respectively diphenylmethane-4, 4' -diisocyanate, tolylene diisocyanate and 1, 5-naphthalene diisocyanate).
3. Three-carbon or four-carbon dihydric alcohol mainly comprises 1, 3-propylene glycol and 1, 4-butanediol.
4. Catalyst: the Sn and N-containing compounds are mainly octyl stannous, dibutyltin dilaurate, N-methyl or N-ethyl morpholine.
5. The blocking agent is an active methylene-containing compound, mainly methyl acetoacetate, ethyl acetoacetate, dialkyl (dimethyl, diethyl, methyl ethyl) malonate, etc.
6. Plasticizers are inactive and include, inter alia, dibutyl phthalate, dioctyl phthalate, dinonyl phthalate, and the like.
7. Solvent: anhydrous toluene, anhydrous xylene, anhydrous ethyl acetate, and the like.
8. Filling: anhydrous superfine talcum powder, anhydrous titanium dioxide, anhydrous super-carbon black and anhydrous white carbon black.
The reaction mechanism is as follows: first, a,
The second step,
Thirdly,
2. Diisocyanate OCN-R1-NCO
3. Three or four carbon diol HO-R2-OH
4. Prepolymer P&
5. Single-component polyurethane PUR
The production process comprises two production processes, wherein the two production processes adopt an air-isolated anhydrous synthesis process, and specifically comprise the following steps:
firstly, a production process of adding a filler comprises the following steps:
accurately weighing various raw materials according to a formula, mixing 35-45 parts (by weight, the same below) of polyether, 8-20 parts of plasticizer and 15-26 parts of filler, grinding, diluting with 15-20 parts of solvent, putting into a kettle, heating to 70-85 ℃, vacuumizing, and distilling to remove water. When dissolvingWhen the water content in the distillate of the agent is less than 4ppm, cooling to 50-55 ℃, slowly adding 4-7.5 parts of aromatic diisocyanate which is melted and diluted by 3-5 parts of anhydrous solvent, gradually heating to 53-65 ℃, reacting for 1-2 hours, then adding 0.02-0.5 part of tri-or tetra-carbon low molecular dihydric alcohol and 0.01-0.2 part of catalyst diluted by 0.8-1 part of solvent, cooling to 50-60 ℃ after reacting for 1-2 hours, adding 0.1-0.6 part of blocking agent diluted by 1.5-2 parts of solvent, adding 0.01-0.3 part of catalyst diluted by 1.5-2 parts of solvent, stirring and cooling to 20-25 ℃, monitoring the viscosity and-NCO content of the product at any time, and when the viscosity reaches 9 x 105～11×105And when the mPAS and-NCO content is 1.7-2.7% of the weight of the product, the product is qualified and taken out of the kettle.
Secondly, synthesizing a prepolymer in advance:
weighing 35-45 parts (by weight, the same applies below) of polyether according to a formula, adding 4-7.5 parts of aromatic diisocyanate diluted by 2-3 parts of anhydrous solvent into a kettle, slowly heating to 53-60 ℃ for reaction for 1-1.5 hours, adding 0.02-0.5 part of tri-or tetra-carbon low-molecular diol, reacting for 1-1.5 hours, cooling to 50-60 ℃, adding 0.1-0.6 part of anhydrous block agent diluted by 0.5-1.0 part of solvent, adding 0.01-0.3 part of catalyst diluted by 0.2-0.5 part of solvent, heating to 55-65 ℃, continuing to react for 1-1.5 hours, cooling to 35-40 ℃, and detecting that the NCO content reaches 1.7-2.7% of the product by weight. Then adding 8-20 parts of anhydrous plasticizer and 15-26 parts of anhydrous filler, uniformly mixing, cooling to 20-25 ℃, and detecting that the viscosity of the product reaches 9 x 105～11×105And taking the mPas out of the kettle for packaging.
The invention has the advantages and positive effects that: the production process of the product is stable, the price of the raw materials is low, all performance indexes of the product reach or exceed the level of like products in the world, and the raw materials are easy to obtain.
The following are specific embodiments of the present invention
Example 1
Raw material weight portion
Average molecular weight in Shenyang chemical plant
5000 of ternary hydroxyl-terminated polyether 42.5
Anhydrous super carbon black 25.5
Dioctyl phthalate 17
1, 3-propanediol 0.1
Diphenylmethane-4, 4' -diisocyanate (MDI) 6.08
Toluene Diisocyanate (TDI) 0.4
Stannous octoate 0.00187
Acetoacetic acid ethyl ester 0.43
Dibutyltin dilaurate 0.26
Toluene 26
Firstly weighing polyether, dioctyl phthalate and medium-super carbon black, uniformly mixing, grinding into fine paste, adding 17 parts of toluene to dilute into a kettle, heating to 70-85 ℃, vacuumizing,cooling to 53 ℃ when the water content in fraction toluene is less than 4ppm, slowly adding MDI (diphenylmethane diisocyanate) and TDI (toluene diisocyanate) solution diluted by 4 parts of toluene, heating to 65 ℃, reacting for 1-2 hours, adding 1, 3-propylene glycol and stannous octoate diluted by 1 part of toluene, reacting for 1 hour, cooling to 55 ℃, adding ethyl acetoacetate diluted by 2 parts of toluene, then adding dibutyltin dilaurate diluted by 2 parts of toluene, uniformly stirring, cooling, and measuring the viscosity to 106The mPas and-NCO content is 1.7-2.7% of the weight of the product, and then the product is taken out of the kettle.
Example 2
Raw material weight portion
Average molecular weight of Shenyang chemical plant
5000 of ternary hydroxyl terminated polyether 38
Water-free super carbon black 22
Dioctyl phthalate 15
1, 3-propanediol 0.06
Diphenylmethane-4, 4' -diisocyanate (MDI) 5.44
Toluene Diisocyanate (TDI) 0.2
Stannous octoate 0.0016
Acetoacetic acid ethyl ester 0.38
Dibutyltin dilaurate 0.23
Toluene 4
Weighing polyether, adding MDI and TDI diluted by 2 parts of anhydrous toluene into a kettle, heating to 53-60 ℃, reacting for 1-2 hours, adding 1, 3-propylene glycol and stannous octoate diluted by 0.5 part of anhydrous toluene, continuing to react for 1.5 hours, cooling to 50 ℃, adding ethyl acetoacetate diluted by 1 part of anhydrous toluene, adding dibutyltin dilaurate diluted by 0.5 part of anhydrous toluene, heating to 55-65 ℃, continuing to react for 1 hour, cooling to 35 ℃, detecting thatthe NCO-content reaches 1.7-2.7% of the product weight, adding anhydrous dioctyl phthalate and anhydrous carbon black, uniformly mixing, cooling to 20-25 ℃, and detecting that the product viscosity reaches 106And taking the mPas out of the kettle for packaging.
Claims (8)
1. A preparation method of a single-component polyurethane adhesive/sealant is characterized by comprising the following steps: firstly, mixing 35-45 parts by weight of hydroxyl-terminated ternary polyether with the molecular weight of 4790-5500, 8-20 parts by weight of plasticizer and 15-26 parts by weight of filler, grinding, adding 18.5-25 parts by weight of solvent to dilute the mixture into a kettle, heating to 70-85 ℃, vacuumizing to remove water by distillation, when the water content of the solvent distillate is less than 4PPm, cooling to 50-55 ℃, slowly adding 4-7.5 parts by weight of aromatic diisocyanate which is melted and diluted by 3-5 parts by weight of anhydrous solvent, gradually heating to 53-65 ℃, reacting for 1-2 hours, adding 0.02-0.5 part by weight of tri-or tetra-carbon dihydric alcohol and 0.01-0.2 part by weight of catalyst diluted by 0.8-1.0 part by weight of solvent, reacting for 1-2 hours, cooling to 50-60 ℃, adding 0.1-0.6 part by weight of active methylene-containing block agent diluted by 1.5-2 parts by weight of solvent, and then adding 0.01-0.3 part by weight of catalyst diluted by 1.5-2 parts by weight of solvent.The measured viscosity is 9 multiplied by 10 when the measured parts are stirred and reduced to 20 to 25 DEG C5～11×105And (3) qualified product discharge is carried out after millipascal seconds and the content of free isocyanate groups accounts for 1.7-2.7% of the weight of the product, and the catalyst is octyl stannous, dibutyltin dilaurate, N-methylmorpholine or N-ethylmorpholine.
2. A preparation method of a single-component polyurethane adhesive/sealant is characterized by comprising the following steps: weighing 35-45 parts by weight of hydroxyl-terminated ternary polyether with the molecular weight of 4790-5500, adding 4-7.5 parts by weight of aromatic diisocyanate diluted by 1.5-2 parts by weight of anhydrous solvent into a kettle, slowly heating to 53-60 ℃, reacting for 1-2 hours, adding 0.02-0.5 part by weight of tri-or tetra-carbon dihydric alcohol and 0.01-0.2 part by weight of catalyst of 0.2-0.5 part by weight of anhydrous solvent, continuing to react for 1-1.5 hours, cooling to 50-60 ℃, adding 0.1-0.6 part by weight of anhydrous active methylene-containing block agent diluted by 0.5-1.0 part by weight of solvent, then adding 0.01-0.3 part by weight of catalyst diluted by 0.2-0.5 part by weight of solvent, heating to 55-65 ℃, continuing to react for 1-1.5 hours, cooling to 35-40 ℃, detecting that the NCO content reaches 1.7-2.7% by weight of the product, adding 20-15 parts by weight of anhydrous plasticizer and 26-15 parts by weight of anhydrous filler, uniformly mixing, cooling to 20-25 ℃, and detecting that the viscosity of the product reaches 9 multiplied by 105～11×105Millipascal second, taking out of the kettle and packaging, wherein the catalyst is octyl stannous or dilauric acidButyl tin, N-methylmorpholine or N-ethylmorpholine.
3. The production method according to claim 1 or 2, characterized in that: wherein the aromatic diisocyanate is diphenylmethane-4, 4' -diisocyanate, toluene diisocyanate or 1, 5-naphthalene diisocyanate.
4. The production method according to claim 1 or 2, characterized in that: wherein the filler is medium-superfine anhydrous carbon black, talcum powder, white carbon black or titanium dioxide.
5. The production method according to claim 1 or 2, characterized in that: wherein the three-carbon or four-carbon dihydric alcohol is 1, 3-propylene glycol or 1, 4-butanediol.
6. The production method according to claim 1 or 2, characterized in that: wherein the solvent is anhydrous toluene, anhydrous xylene or anhydrous ethyl acetate.
7. The production method according to claim 1 or 2, characterized in that: wherein the active methylene-containing block agent is methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate or methyl ethyl malonate.
8. The production method according to claim 1 or 2, characterized in that: wherein the plasticizer is dibutyl phthalate, dioctyl phthalate or dinonyl phthalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100755A CN1048517C (en) | 1997-02-21 | 1997-02-21 | Method for preparing single component polyurethane adhesive/seal gum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100755A CN1048517C (en) | 1997-02-21 | 1997-02-21 | Method for preparing single component polyurethane adhesive/seal gum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1161362A CN1161362A (en) | 1997-10-08 |
| CN1048517C true CN1048517C (en) | 2000-01-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97100755A Expired - Fee Related CN1048517C (en) | 1997-02-21 | 1997-02-21 | Method for preparing single component polyurethane adhesive/seal gum |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075103C (en) * | 1998-09-21 | 2001-11-21 | 深圳市奥博胶粘剂化工有限公司 | Polyurethane adhesives/sealant composition, precursor and preparation process thereof |
| CN1079418C (en) * | 1999-03-12 | 2002-02-20 | 金坛市胶粘剂厂 | Special adhesive for composite shielding ribbon of polyurethane cable and its production process |
| CN1079419C (en) * | 1999-03-12 | 2002-02-20 | 金坛市胶粘剂厂 | Composite dry adhesive for high temperature steamed polyurethane bag and its production process |
| JP5170499B2 (en) * | 2006-08-18 | 2013-03-27 | 日本ポリウレタン工業株式会社 | Emulsion composition containing blocked isocyanate, method for producing the same, and composition for baking type paint or adhesive |
| CN101434825B (en) * | 2008-12-12 | 2010-05-12 | 河南永丽化工有限公司 | Bicomponent terminal mercapto polyurethane mildewproof sealant and preparation thereof |
| CN101812228B (en) * | 2009-02-24 | 2012-10-24 | 高鼎精细化工(昆山)有限公司 | All toluene solvent type polyurethane resin and preparation method thereof |
| CN101792638A (en) * | 2010-03-16 | 2010-08-04 | 上海亚斯电气制造有限公司 | Single-component polyurethane underwater sealing self-curing waterproof anticorrosive marine glue and preparation method thereof |
| CN101885957A (en) * | 2010-07-09 | 2010-11-17 | 山东北方现代化学工业有限公司 | Room-temperature moisture cured one-component water-expansion polyurethane sealant |
| CN102000654B (en) * | 2010-09-03 | 2016-05-11 | 上海德联化工有限公司 | Vehicle glass glue painting method |
| CN106833489A (en) * | 2015-12-04 | 2017-06-13 | 中国人民解放军军械工程学院 | A kind of double-component silicane-modified polyurethane fluid sealant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54126297A (en) * | 1978-03-24 | 1979-10-01 | Sansutaa Kagaku Kougiyou Kk | Sealing material composition |
| JPH02169615A (en) * | 1988-12-22 | 1990-06-29 | Mitsui Toatsu Chem Inc | Flexible, high-strength urethane binder |
| EP0460328A1 (en) * | 1990-06-05 | 1991-12-11 | Minnesota Mining And Manufacturing Company | Polyurethane prepolymer composition comprising a water-immiscible solvent |
| CN1091765A (en) * | 1994-01-18 | 1994-09-07 | 吉林省华详实业公司 | Polyurethane binder/sealant and making method |
-
1997
- 1997-02-21 CN CN97100755A patent/CN1048517C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54126297A (en) * | 1978-03-24 | 1979-10-01 | Sansutaa Kagaku Kougiyou Kk | Sealing material composition |
| JPH02169615A (en) * | 1988-12-22 | 1990-06-29 | Mitsui Toatsu Chem Inc | Flexible, high-strength urethane binder |
| EP0460328A1 (en) * | 1990-06-05 | 1991-12-11 | Minnesota Mining And Manufacturing Company | Polyurethane prepolymer composition comprising a water-immiscible solvent |
| CN1091765A (en) * | 1994-01-18 | 1994-09-07 | 吉林省华详实业公司 | Polyurethane binder/sealant and making method |
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| CN1161362A (en) | 1997-10-08 |
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