CN102424704B - Modified water-dispersible polyisocyanate - Google Patents
Modified water-dispersible polyisocyanate Download PDFInfo
- Publication number
- CN102424704B CN102424704B CN2011102511864A CN201110251186A CN102424704B CN 102424704 B CN102424704 B CN 102424704B CN 2011102511864 A CN2011102511864 A CN 2011102511864A CN 201110251186 A CN201110251186 A CN 201110251186A CN 102424704 B CN102424704 B CN 102424704B
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- CN
- China
- Prior art keywords
- dispersible polyisocyanate
- tmp
- dissolving
- modified water
- mdi
- 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.)
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- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 11
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 11
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 13
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 239000012263 liquid product Substances 0.000 claims abstract description 4
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 11
- BPMDNHQFWDPPMJ-UHFFFAOYSA-N 3,3-dihydroxy-2,2-dimethylpropanoic acid Chemical compound OC(O)C(C)(C)C(O)=O BPMDNHQFWDPPMJ-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 150000002466 imines Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 125000005474 octanoate group Chemical group 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 2
- 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 abstract 2
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 abstract 2
- 229960001082 trimethoprim Drugs 0.000 abstract 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydroxy carboxylic acid compound Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses modified water-dispersible polyisocyanate. The modified water-dispersible polyisocyanate is prepared through the following steps: a, dissolving TMP (trimethoprim) and dyhydroxytrimethylacetic acid in methyl isobutyl ketone, heating to 40 DEG C, and stirring for dissolving; b, adding MDI (diphenylmethane diisocyanate), methyl isobutyl ketone and a composite catalyst which are weighed into a reaction kettle, and heating to 40 DEG C for completely dissolution; c, then slowly adding the solution obtained in the step a for 0.5 hour-5 hours, heating to 50-90 DEG C and then insulating and reacting for 0.5 hour-5 hours; d, subsequently, reducing the temperature to be less than 30 DEG C, slowly adding N,N-dimethylethanolamine for neutralization reaction, and stirring for 0.5 hour; and e, finally, adding weighed deionized water, and cooling to room temperature, so as to obtain a light yellow transparent liquid product. The modified water-dispersible polyisocyanate is more environmentally-friendly and has less human health damage.
Description
Technical field
The present invention relates to a kind of stable water-based polyisocyanates and preparation method thereof.
Background technology
Performed polymer with the NCO end group is very important intermediate during urethane synthesizes, because the NCO performed polymer can form the crosslinking structure thing and use as crosslinked bridging agent with hydroxyl, carboxyl, the amino groups reaction of band for the chemical combination of various ripple hydrogen alive, traditional linking agent is difficult to direct emulsification or is scattered in water, improve the wetting ability of polymeric polyisocyanate by introducing hydrophilic radical, make it be easy to emulsification or dispersion in water, thereby keep certain stability.As U.S. Patent No. 4,433,095 and CN101316874A.
Summary of the invention
The object of the invention is to, a kind of low-free TDI content is provided, the novel bridging agent that water dispersible is good, this bridging agent storage-stable, heat treatment performance is remarkable, is suitable for suitability for industrialized production.
For realizing the purpose of foregoing invention, in the present invention, novel bridging agent prepares by the following technical solutions: a kind of water dispersible polyisocyanate of modification prepares by following steps:
A, TMP and dihydroxyl trimethylacetic acid are dissolved in methyl iso-butyl ketone (MIBK), and are heated to 40 ℃, stirring and dissolving;
B, the MDI that adds metering in reactor, methyl iso-butyl ketone (MIBK) and composite catalyst are warming up to 40 ℃, fully dissolving; Described composite catalyst is by two stannous octoates and composite the forming of anilino imines nickel;
C, the solution that then slowly adds step a to obtain, this adding procedure time is 0.5h～5h, and is heated to 50～90 ℃ of lower insulation reaction 0.5h～5h;
D, then reduce the temperature to below 30 ℃, slowly add N, the N-dimethylethanolamine carries out neutralization reaction, and stirs 0.5h,
E, add at last the deionized water of metering, be cooled to room temperature, obtain the light yellow transparent liquid product.
Mole proportioning of MDI and TMP is 1～2:1.
The mol ratio of described TMP and dihydroxyl trimethylacetic acid is 1:0.2～1.
Described composite catalyzing agent concentration is 800～2000ppm.
Beneficial effect: the present invention has the following advantages with respect to prior art:
we by experiment, MDI-TMP type bridging agent is being carried out on the basis of modification, by introducing another kind of hydrophilic reagent hydroxy carboxylic acid compound, adjust each processing parameter, want to seek a kind of aqueous dispersion type bond strength promotor, laking agent, solid, pigment is anti-dyes the agent that makes progress of friction washing fastness, the effect that object being treated is all had the enhancing of building bridge, drying, thermal treatment just can be brought into play remarkable performance, and can be widely used in water-borne coatings, the crosslinked bridging agent of dyestuff is owing to adopting MDI, TMP etc. are as raw material, make the water dispersible polyisocyanate environmental protection more of the modification of acquisition, less to the HUMAN HEALTH injury, the present invention adopts composite catalyst to carry out prepolymerization reaction, can improve combined coefficient, reduces the polymerization difficulty.
Embodiment
Below in conjunction with embodiment, the present invention is done further describing in detail, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment:
In the cleaning drying and during the container of condenser is housed, add TMP (1.00kmol), dihydroxyl trimethylacetic acid (0.5kmol) and methyl isobutyl ketone solvent, be mixed with the solution of 75% left and right, be warming up to 40 ℃-50 ℃, abundant stirring and dissolving is after thing to be mixed dissolves fully, stop stirring, 40 ℃-50 ℃ of system temperature maintenances are stand-by.
in the reactor of cleaning drying, condenser is installed, vacuumatic measuring adds MDI(5.5kmol), methyl iso-butyl ketone (MIBK) and composite catalyst 3.00kg, be mixed with the solution of 75% left and right, shut the large lid of hand-hole after complete, start and stir and slowly be warming up to 60 ℃, treat that it dissolves fully, under the condition of 60 ℃ of temperature, slowly drip the mixed solution of TMP and dihydroxyl trimethylacetic acid, dropping temperature is controlled at 60 ℃-85 ℃, time for adding is controlled at 1h-2.5h, after dripping end, at 85 ℃-95 ℃ reaction 1.5h, drip the N that measures under lower than 80 ℃, N-dimethylethanolamine (0.55kmol) neutralizes, stir 0.5h, add deionized water (687kg), be cooled to room temperature, obtain faint yellow transparent dispersion liquid product, solids content 39.50%, viscosity 〉=1570mPa.s, pH value: approximately 9.0.Described composite catalyst is composite the forming of ratio of 2:0.5 according to mol ratio by two stannous octoates and anilino imines nickel.
Claims (2)
1. the water dispersible polyisocyanate of a modification is characterized in that: prepare by following steps: a, TMP and dihydroxyl trimethylacetic acid are dissolved in methyl iso-butyl ketone (MIBK), and are heated to 40 ℃, stirring and dissolving; B, the MDI that adds metering in reactor, methyl iso-butyl ketone (MIBK) and composite catalyst are warming up to 40 ℃, fully dissolving; Described composite catalyst is by two stannous octoates and composite the forming of anilino imines nickel; C, the solution that then slowly adds step a to obtain, this adding procedure time is 0.5h～5h, and is heated to 50～90 ℃ of lower insulation reaction 0.5h～5h; D, then reduce the temperature to below 30 ℃, slowly add N, the N-dimethylethanolamine carries out neutralization reaction, and stirs 0.5h, e, adds at last the deionized water of metering, is cooled to room temperature, obtains the light yellow transparent liquid product; Mole proportioning of MDI and TMP is 1～2:1; The mol ratio of described TMP and dihydroxyl trimethylacetic acid is 1:0.2～1.
2. the water dispersible polyisocyanate of modification according to claim 1, it is characterized in that: the composite catalyzing agent concentration is 800～2000ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102511864A CN102424704B (en) | 2011-08-30 | 2011-08-30 | Modified water-dispersible polyisocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102511864A CN102424704B (en) | 2011-08-30 | 2011-08-30 | Modified water-dispersible polyisocyanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102424704A CN102424704A (en) | 2012-04-25 |
| CN102424704B true CN102424704B (en) | 2013-05-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102511864A Expired - Fee Related CN102424704B (en) | 2011-08-30 | 2011-08-30 | Modified water-dispersible polyisocyanate |
Country Status (1)
| Country | Link |
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| CN (1) | CN102424704B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105802321B (en) * | 2014-12-30 | 2018-07-06 | 立邦涂料（天津）有限公司 | A kind of cleaning solvent of electrophoretic coating production of resins equipment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801644A (en) * | 1985-10-04 | 1989-01-31 | Polyvinyl Chemicals Inc. | Coating compositions |
| CN1611522A (en) * | 2003-10-29 | 2005-05-04 | 深圳彩虹环保建材科技有限公司 | Method for preparing water-based polyurethane |
| CN101456942A (en) * | 2008-12-30 | 2009-06-17 | 南京工业大学 | Water-soluble polyurethane and cementing compound containing water-soluble polyurethane and use thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010095665A1 (en) * | 2009-02-18 | 2010-08-26 | 東ソー株式会社 | Aqueous polyurethane resin composition and film articles using same |
-
2011
- 2011-08-30 CN CN2011102511864A patent/CN102424704B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801644A (en) * | 1985-10-04 | 1989-01-31 | Polyvinyl Chemicals Inc. | Coating compositions |
| CN1611522A (en) * | 2003-10-29 | 2005-05-04 | 深圳彩虹环保建材科技有限公司 | Method for preparing water-based polyurethane |
| CN101456942A (en) * | 2008-12-30 | 2009-06-17 | 南京工业大学 | Water-soluble polyurethane and cementing compound containing water-soluble polyurethane and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| MDI基水性聚氨酯胶粘剂的合成与性能研究;刘都宝等;《印染助剂》;20081031;第25卷(第10期);25-27 * |
| 刘都宝等.MDI基水性聚氨酯胶粘剂的合成与性能研究.《印染助剂》.2008,第25卷(第10期),25-27. |
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| Publication number | Publication date |
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| CN102424704A (en) | 2012-04-25 |
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| C14 | Grant of patent or utility model | ||
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Owner name: SUZHOU FANGYOU NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: WUJIANG BEISHE SHENGYUAN TEXTILE AUXILIARIES FACTORY Effective date: 20131120 |
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Free format text: CORRECT: ADDRESS; FROM: 215214 SUZHOU, JIANGSU PROVINCE TO: 215200 SUZHOU, JIANGSU PROVINCE |
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Effective date of registration: 20131120 Address after: 215200, Changan Road, Wujiang economic and Technological Development Zone, Jiangsu, Suzhou province (Science and Technology Pioneer Park) Patentee after: SUZHOU FANGYOU NEW MATERIAL CO., LTD. Address before: 215214 Jiangsu city of Suzhou province Wujiang city FENHU Economic Development Zone Beishe catalpa Chemical District Patentee before: Wujiang Beishe Shengyuan Textile Auxiliaries Factory |
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Effective date of registration: 20151013 Address after: Song Ling Zhen Wujiang District of Suzhou City, Jiangsu province 215200 Suzhou River Road No. 18 Patentee after: Suzhou Xielv Network Technology Co., Ltd. Address before: 215200, Changan Road, Wujiang economic and Technological Development Zone, Jiangsu, Suzhou province (Science and Technology Pioneer Park) Patentee before: SUZHOU FANGYOU NEW MATERIAL CO., LTD. |
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| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 215200 Shengze, Jiangsu, China Town, Shengze, West No. two ring road, No. 1188, China Textile Science and Technology Park, Wujiang, building 10 Patentee after: Suzhou Xielv Network Technology Co., Ltd. Address before: Song Ling Zhen Wujiang District of Suzhou City, Jiangsu province 215200 Suzhou River Road No. 18 Patentee before: Suzhou Xielv Network Technology Co., Ltd. |
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Granted publication date: 20130515 Termination date: 20170830 |
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