CN102352015A - Improved method for preparing environment-friendly diphenylmethane diisocyanate-trimethylolpropane (MDI-TMP) curing agent - Google Patents
Improved method for preparing environment-friendly diphenylmethane diisocyanate-trimethylolpropane (MDI-TMP) curing agent Download PDFInfo
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- CN102352015A CN102352015A CN2011102459973A CN201110245997A CN102352015A CN 102352015 A CN102352015 A CN 102352015A CN 2011102459973 A CN2011102459973 A CN 2011102459973A CN 201110245997 A CN201110245997 A CN 201110245997A CN 102352015 A CN102352015 A CN 102352015A
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Abstract
The invention discloses an improved method for preparing an environment-friendly diphenylmethane diisocyanate-trimethylolpropane (MDI-TMP) curing agent, which comprises the following steps of: a, preparing an MDI solution, namely adding ethyl acetate into a reaction kettle filled with nitrogen or carbon dioxide, adding MDI and a small amount of catalyst, raising the temperature to be between 50 and 60 DEG C, stirring until the MDI is completely dissolved, and preserving heat for 1 to 2 hours; b, preparing a TMP solution, namely adding the ethyl acetate into an another container, adding TMP, raising the temperature to be between 40 and 50 DEG C, and stirring until the TMP is completely dissolved to obtain the TMP solution; and c, adding the TMP solution into the MDI solution in the step a, preserving heat at the temperature of 70 DEG C, reacting for 1 to 5 hours, and adding a small amount of polymerization inhibitor, wherein an antioxidant is also needed to be added into the step a and is 2,6-di-tert-butyl-4-methylphenol or ascorbic acid. The MDI-TMP curing agent product prepared by the method is water white transparent liquid, is not discolored after being placed and stored for a long time, and has a long anti-discoloring period.
Description
Technical field
The invention belongs to chemical field, relate in particular to the preparation method of MDI-TMP solidifying agent.
Background technology
Polyurethane coating is one type of excellent property, widely used coating.Because therefore its paint film good mechanical property, tough and tensile, wear-resisting, plentiful, bright can have the wide application of sending out in the field at coatings decoration, synthon in low-temperature curing.Solidifying agent is the important component part in the double-component polyurethane coating; And TDI-TMP type solidifying agent is wherein most widely used a kind of; But because the TDI monomer of TDI-TMP solidifying agent is a kind of noxious chemical; In use inevitably there is free TDI; 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%; Along with the enhancing of environmental protection consciousness, how reducing free TDI content is a present trend with the TDI-TMP solidifying agent that obtains environment-friendly type.And the solidifying agent of MDI-TMP type is because its hypotoxicity; More and more paid close attention to; Especially the preparation method is updating always, and the MDI-TMP solidifying agent that common working method obtains is light yellow transparent liquid or yellow transparent liquid, and this is oxidized and cause in reaction process.But in application process, hope that again the coating make is transparent, so xanchromatic MDI-TMP solidifying agent receives application limitations, in addition, even the white transparent solidifying agent that obtains, also oxidation stain gradually easily in storage process, thus cause product failure.
Summary of the invention
Goal of the invention: to the defective of above-mentioned existence, it is transparent to the invention provides a kind of preparation water white, and the method for the MDI-TMP solidifying agent of the look that remains unchanged for a long period of time.
Technical scheme: for realizing the foregoing invention purpose; The present invention adopts following technical scheme: a kind of improved environment-friendly type MDI-TMP solidifying agent preparation method; May further comprise the steps: the preparation of a, MDI solution: in the reaction kettle that is full of nitrogen or carbonic acid gas, add vinyl acetic monomer; Add MDI again; Be warming up to 50 ~ 60 ℃; Be stirred to dissolving fully simultaneously, and be incubated 1 ~ 2h; The preparation of b, TMP solution: in other container, add vinyl acetic monomer or, add TMP again, be warming up to 40 ~ 50 ℃, being stirred to fully, dissolving obtains TMP solution; C, in MDI solution, add TMP solution described in the step a, 70 ℃ of following insulation reaction 1 ~ 5 hour, also to add antioxidant among the said step a; Described antioxidant is 2,6-di-tert-butyl-4-methy phenol or xitix.
Said antioxidant is to dissolve the back fully at MDI to add; The add-on of said antioxidant is 0.1 ~ 1% of a MDI weight.
Also to add catalyzer among the said step a; Said catalyzer is Lithium Oxide 98min, epoxyeicosatrienoic acid zinc or dodecyl dimethyl tertiary amine.
Also to add stopper among the said step c; Said stopper is phosphoric acid, oxalic acid or Hydrocerol A.
Beneficial effect: compared with prior art, the present invention has the following advantages: when TMP and MDI building-up reactions, add antioxidant and can prevent MDI-TMP solidifying agent variable color in the preservation process of preparing, thereby have the long anti-discolouring phase.
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; MDI and the little amount of catalyst oxidation reason that adds 30 parts again is warming up to 50 ~ 60 ℃, be stirred to dissolving fully simultaneously after; Add 0.2 part 2, the 6-di-tert-butyl-4-methy phenol is as antioxidant, and be incubated 1 ~ 2h and obtain MDI solution; In 10 parts vinyl acetic monomer, add 10 parts of TMP in addition, be warming up to 40 ~ 50 ℃, being stirred to fully, dissolving obtains TMP solution; In MDI solution, slowly drip TMP solution then, the time of this dropping process is 1 ~ ~ 2 hour, 70 ℃ of following insulation reaction 4 hours, adds a spot of stopper phosphoric acid then at last.
Through detecting, the technical indicator of gained MDI-TMP solidifying agent is following: outward appearance is the water white transparent liquid under the normal temperature, and solid content is 73%, and viscosity is 1455mPa.s, and-NCO content is 11.0 ~ 11.5%, and the free TDI monomer content is less than 0.05%.The MDI-TMP solidifying agent that obtains all occurs solidifying through depositing 1 year, and viscosity is about 1500 mPa.s, and outward appearance water white transparence liquid not yet, and not seeing has colour-change.
Embodiment 2 ~ 3
| ? | Antioxidant | Catalyzer | Stopper |
| Embodiment 2 | 2,6-di-tert-butyl-4-methy phenol | Epoxyeicosatrienoic acid zinc | Phosphoric acid |
| Embodiment 3 | Xitix | The dodecyl dimethyl tertiary amine | Oxalic acid |
Table 1 is antioxidant, catalyzer and the stopper that adds among the embodiment 2 ~ 3
The step of preparation process of embodiment 2 ~ 3 and embodiment 1 are basic identical, and it is to have added different antioxidants, catalyzer and stopper with the difference of embodiment 1, and is specifically as shown in table 1.
Claims (4)
1. improved environment-friendly type MDI-TMP solidifying agent preparation method; May further comprise the steps: the preparation of a, MDI solution: in the reaction kettle that is full of nitrogen or carbonic acid gas, add vinyl acetic monomer, add MDI again, be warming up to 50 ~ 60 ℃; Be stirred to dissolving fully simultaneously, and be incubated 1 ~ 2h; The preparation of b, TMP solution: in other container, add vinyl acetic monomer or, add TMP again, be warming up to 40 ~ 50 ℃, being stirred to fully, dissolving obtains TMP solution; C, in MDI solution, add TMP solution described in the step a, 70 ℃ of following insulation reaction 1 ~ 5 hour, it is characterized in that: also will add antioxidant among the said step a; Described antioxidant is 2,6-di-tert-butyl-4-methy phenol or xitix.
2. improved environment-friendly type MDI-TMP solidifying agent preparation method according to claim 1, work being characterised in that: said antioxidant is to dissolve the back fully at MDI to add; The add-on of said antioxidant is 0.1 ~ 1% of a MDI weight.
3. improved environment-friendly type MDI-TMP solidifying agent preparation method according to claim 2 is characterized in that: also will add catalyzer among the said step a; Said catalyzer is Lithium Oxide 98min, epoxyeicosatrienoic acid zinc or dodecyl dimethyl tertiary amine.
4. improved environment-friendly type MDI-TMP solidifying agent preparation method according to claim 3 is characterized in that: also will add stopper among the said step c; Said stopper is phosphoric acid, oxalic acid or Hydrocerol A.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102459973A CN102352015A (en) | 2011-08-25 | 2011-08-25 | Improved method for preparing environment-friendly diphenylmethane diisocyanate-trimethylolpropane (MDI-TMP) curing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102459973A CN102352015A (en) | 2011-08-25 | 2011-08-25 | Improved method for preparing environment-friendly diphenylmethane diisocyanate-trimethylolpropane (MDI-TMP) curing agent |
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| CN102352015A true CN102352015A (en) | 2012-02-15 |
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| CN2011102459973A Pending CN102352015A (en) | 2011-08-25 | 2011-08-25 | Improved method for preparing environment-friendly diphenylmethane diisocyanate-trimethylolpropane (MDI-TMP) curing agent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352019A (en) * | 2011-08-30 | 2012-02-15 | 吴江市北厍盛源纺织品助剂厂 | Environment-friendly MDI-TMP polymerization inhibitor |
| CN103145947A (en) * | 2013-02-25 | 2013-06-12 | 晋江市华福化工有限公司 | Novel environmental-friendly curing agent and preparation method for same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357558A (en) * | 2000-12-05 | 2002-07-10 | 上海市涂料研究所 | Paint curing agent 4,4'-diphenyl methane diisocyanate prepolymer and its prepn |
| CN101230124A (en) * | 2007-01-27 | 2008-07-30 | 周建明 | Curing agent 4,4'-biphenyl methane diisocyanate prepolymer and preparation method thereof |
-
2011
- 2011-08-25 CN CN2011102459973A patent/CN102352015A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357558A (en) * | 2000-12-05 | 2002-07-10 | 上海市涂料研究所 | Paint curing agent 4,4'-diphenyl methane diisocyanate prepolymer and its prepn |
| CN101230124A (en) * | 2007-01-27 | 2008-07-30 | 周建明 | Curing agent 4,4'-biphenyl methane diisocyanate prepolymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《涂料工业》 20100731 周俊峰 等 环保型双组分聚氨酯固化剂MDI/TMP的开发及应用 第21-24页 1-4 第40卷, 第7期 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352019A (en) * | 2011-08-30 | 2012-02-15 | 吴江市北厍盛源纺织品助剂厂 | Environment-friendly MDI-TMP polymerization inhibitor |
| CN103145947A (en) * | 2013-02-25 | 2013-06-12 | 晋江市华福化工有限公司 | Novel environmental-friendly curing agent and preparation method for same |
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Application publication date: 20120215 |