CN102391469A - MDI-TMP (diphenyl-methane-diisocyanate-trimethylolpropane) type polyurethane prepolymer with high end-capping rate - Google Patents
MDI-TMP (diphenyl-methane-diisocyanate-trimethylolpropane) type polyurethane prepolymer with high end-capping rate Download PDFInfo
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- CN102391469A CN102391469A CN2011102460203A CN201110246020A CN102391469A CN 102391469 A CN102391469 A CN 102391469A CN 2011102460203 A CN2011102460203 A CN 2011102460203A CN 201110246020 A CN201110246020 A CN 201110246020A CN 102391469 A CN102391469 A CN 102391469A
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- Prior art keywords
- mdi
- tmp
- type polyurethane
- high end
- blocking rate
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- 229920001730 Moisture cure polyurethane Polymers 0.000 title abstract description 3
- NWJKYWNQIWUXJV-UHFFFAOYSA-N CCC(CO)(CO)CO.N=C=O.N=C=O.C(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound CCC(CO)(CO)CO.N=C=O.N=C=O.C(C1=CC=CC=C1)C1=CC=CC=C1 NWJKYWNQIWUXJV-UHFFFAOYSA-N 0.000 title abstract 2
- 229920002635 polyurethane Polymers 0.000 claims abstract description 15
- 239000004814 polyurethane Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 11
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical group 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000006378 damage Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract 1
- 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 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Abstract
The invention discloses an MDI-TMP (diphenyl-methane-diisocyanate-trimethylolpropane) type polyurethane prepolymer with high end-capping rate, which is prepared by a method comprising the following steps: a) adding an organic solvent and MDI into a reaction kettle filled with nitrogen or carbon dioxide, heating, stirring and dissolving; b) adding TMP into solution obtained in the step a), and performing heating reaction for 1-4 hours to get a pre-polymerization product; and c) performing end-capping reaction: adding an end-capping agent and an accelerating agent in the pre-polymerization product obtained in the step b), reacting for 1-2 hours, and finally regulating the pH value to 5-7 for preparation. By adopting the low-toxicity MDI, the content of free TDI (toluene diisocyanate) is greatly reduced, and the harm to the health of a human body is further reduced; and the end-capping rate of a polyurethane product is simultaneously greatly improved.
Description
Technical field
The invention belongs to chemical field, relate in particular to the aqurous ployurethane performed polymer.
Background technology
Urethane is because therefore its paint film good mechanical property, tough and tensile, wear-resisting, plentiful, bright can have purposes widely, especially in synthon and textile finshing agent field in low-temperature curing.Aqurous ployurethane is medium with water, and safety is nonflammable, has kept the premium properties of conventional solvent type polyurethane, can give the good pliability of fabric, fullness ratio, washable, wear-resisting, performance such as rebound resilience is good, smooth simultaneously.But traditional aqurous ployurethane all is to adopt TDI (tolylene diisocyanate) and TMP (TriMethylolPropane(TMP)) to synthesize to obtain; But TDI is very big to human harm; The free TDI content of the TDI-TMP type bridging agent of domestic production at present is many 2 ~ 5%; And the isocyanate groups in the general base polyurethane prepolymer for use as is a very active functional group, loses activity thereby possibly react with water base plinth, and the physical and chemical performance of urethane is had a negative impact.In order to make in its stable existence water, easy to use, adopt end-capping reagent that isocyanate groups is sealed usually, to form stable compound, in use through appropriate heat treatment, the unpacking reaction takes place, be that NCO recovers activity.But the end-blocking rate of general urethane end-blocking agent is lower, has only about 20%.
Summary of the invention
Goal of the invention:, the invention provides the water-soluble MDI-TMP type polyurethane performed polymer that adopts MDI (4, the 4-'-diphenylmethane diisocyanate) and TMP (TriMethylolPropane(TMP)) preparation to the defective of above-mentioned existence.
Technical scheme: for realizing the foregoing invention purpose; The present invention adopts following technical scheme: a kind of high end-blocking rate MDI-TMP type polyurethane performed polymer; It is characterized in that making: a, in the reaction kettle that is full of nitrogen or carbonic acid gas, add organic solvent and MDI, through heating and stirring and dissolving through following steps; B, in the solution that step a obtains, add TMP, reacting by heating 1 ~ 4h obtains prepolymer product; C, in step b, obtain to add end-capping reagent and promotor in the prepolymer product, and react 1 ~ 2h, regulating the pH value at last is 5 ~ 7, gets final product.
Promotor described in the said step c is triethylamine or S-WAT.
As the improvement to technique scheme, organic solvent is vinyl acetic monomer, ETHYLE ACETATE, Virahol or polyether glycol among the said step a; Said Heating temperature is 40 ~ 60 ℃.
As the improvement to technique scheme, among the said step b, the mol ratio of MDI and TMP is 2 ~ 4:1,50 ~ 80 ℃ of temperature of reaction, and the reaction times is 4h.
As the improvement to technique scheme, end-capping reagent is phenols or inorganic acids among the said step c.
As the improvement to technique scheme, said end-capping reagent is a sodium sulfite anhy 96.
As the improvement to technique scheme, the material of regulating pH among the said step c is phosphoric acid or sulfuric acid.
Beneficial effect: compared with prior art, the present invention has the following advantages: owing to adopt the MDI of low toxicity, free TDI content reduces greatly, thereby has reduced the injury to HUMAN HEALTH; Add promotor simultaneously, improved the end-blocking rate of polyurethane product greatly.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is elaborated, but protection scope of the present invention is not limited to said embodiment.
Embodiment 1
The vinyl acetic monomer that in being full of the reaction kettle of nitrogen, adds 15 parts adds 30 parts MDI again, is warming up to 50 ℃; After being stirred to fully dissolving simultaneously, add 15 parts TMP, and under the elevated temperature to 70 ℃; Reacted 4 hours; The sodium sulfite anhy 96 that adds 30 parts then, 10 parts S-WAT, and reacted 2 hours; Adding a spot of phosphoric acid adjusting pH at last is 4.5.
Through detecting, the technical indicator of gained MDI-TMP bridging agent is following: outward appearance is the water white transparent liquid under the normal temperature, and solid content is 56%, and viscosity is 1304mPa.s, and-NCO content is 11.0 ~ 11.5%, and the free TDI monomer content is less than 0.05%; End-blocking rate through iodine molecule titration measuring polyurethane product is greater than 90%.
Embodiment 2 ~ 3
The step of preparation process of embodiment 2 ~ 3 is identical with embodiment, and the different MDI that just add are different with TMP ratio, end-capping reagent, pH regulator agent and reaction parameter.Table 1 is MDI and TMP ratio, end-capping reagent, pH regulator agent and the reaction parameter that adds among the embodiment 2 ~ 3.
Embodiment 2 and 3, employing all be S-WAT, through the test polyurethane product the end-blocking rate also greater than 90%.
Claims (7)
1. one kind high end-blocking rate MDI-TMP type polyurethane performed polymer is characterized in that making through following steps: a, in the reaction kettle that is full of nitrogen or carbonic acid gas, add organic solvent and MDI, through heating and stirring and dissolving; B, in the solution that step a obtains, add TMP, reacting by heating 1 ~ 4h obtains prepolymer product; C, end capping: in step b, obtain to add end-capping reagent and promotor in the prepolymer product, and react 1 ~ 2h, regulating the pH value at last is 5 ~ 7, gets final product.
2. high end-blocking rate MDI-TMP type polyurethane performed polymer according to claim 1, it is characterized in that: promotor described in the step c is triethylamine or S-WAT.
3. high end-blocking rate MDI-TMP type polyurethane performed polymer according to claim 2, it is characterized in that: organic solvent is vinyl acetic monomer, ETHYLE ACETATE, Virahol or polyether glycol among the said step a; Said Heating temperature is 40 ~ 60 ℃.
4. high end-blocking rate MDI-TMP type polyurethane performed polymer according to claim 3, it is characterized in that: among the said step b, the mol ratio of MDI and TMP is 2 ~ 4:1,50 ~ 80 ℃ of temperature of reaction, the reaction times is 4h.
5. high end-blocking rate MDI-TMP type polyurethane performed polymer according to claim 4, it is characterized in that: end-capping reagent is phenols or inorganic acids among the said step c.
6. high end-blocking rate MDI-TMP type polyurethane performed polymer according to claim 5, it is characterized in that: said end-capping reagent is a sodium sulfite anhy 96.
7. high end-blocking rate MDI-TMP type polyurethane performed polymer according to claim 6 is characterized in that: the material of regulating pH among the said step c is phosphoric acid or sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102460203A CN102391469B (en) | 2011-08-25 | 2011-08-25 | MDI-TMP (diphenyl-methane-diisocyanate-trimethylolpropane) type polyurethane prepolymer with high end-capping rate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102460203A CN102391469B (en) | 2011-08-25 | 2011-08-25 | MDI-TMP (diphenyl-methane-diisocyanate-trimethylolpropane) type polyurethane prepolymer with high end-capping rate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102391469A true CN102391469A (en) | 2012-03-28 |
| CN102391469B CN102391469B (en) | 2013-01-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102460203A Expired - Fee Related CN102391469B (en) | 2011-08-25 | 2011-08-25 | MDI-TMP (diphenyl-methane-diisocyanate-trimethylolpropane) type polyurethane prepolymer with high end-capping rate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1704523A (en) * | 2004-05-27 | 2005-12-07 | 香港理工大学 | Reactive aqueous polyurethane fabric finishing agent, its preparation method and application |
| CN101638471A (en) * | 2009-09-01 | 2010-02-03 | 陕西科技大学 | Method for preparing water-base cation blocked polyisocyanates crosslinking and curing agent |
| CN101824135A (en) * | 2010-04-13 | 2010-09-08 | 江苏工业学院 | Preparation method and application of terminated-type cation water-borne polyurethane color fixing agent |
-
2011
- 2011-08-25 CN CN2011102460203A patent/CN102391469B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1704523A (en) * | 2004-05-27 | 2005-12-07 | 香港理工大学 | Reactive aqueous polyurethane fabric finishing agent, its preparation method and application |
| CN101638471A (en) * | 2009-09-01 | 2010-02-03 | 陕西科技大学 | Method for preparing water-base cation blocked polyisocyanates crosslinking and curing agent |
| CN101824135A (en) * | 2010-04-13 | 2010-09-08 | 江苏工业学院 | Preparation method and application of terminated-type cation water-borne polyurethane color fixing agent |
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| Publication number | Publication date |
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| CN102391469B (en) | 2013-01-09 |
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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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| CF01 | Termination of patent right due to non-payment of annual fee | ||
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Granted publication date: 20130109 Termination date: 20170825 |