CN102492115B - Preparation method for blocked MDI (diphenylmethane diisocyanate)-TMP (trimethylolpropane).F cross linking agent - Google Patents
Preparation method for blocked MDI (diphenylmethane diisocyanate)-TMP (trimethylolpropane).F cross linking agent Download PDFInfo
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- CN102492115B CN102492115B CN201110338550.0A CN201110338550A CN102492115B CN 102492115 B CN102492115 B CN 102492115B CN 201110338550 A CN201110338550 A CN 201110338550A CN 102492115 B CN102492115 B CN 102492115B
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Abstract
The invention discloses a preparation method for a blocked MDI (diphenylmethane diisocyanate)-TMP (trimethylolpropane).F cross linking agent, which utilizes ethyl acetate as organic solvent and TMP and MDI as organic ingredients. The method includes the steps of synthesizing MDI-TMP prepolymer which is a yellow transparent liquor product at the temperature of 30-120 DEG C under the action of a di-stannous octoate catalyst; and then enclosing the synthesized MDI-TMP prepolymer with phenol serving as blocking agent at the temperature of 40-100 DEG C, so that MDI-TMP.F cross linking agent which is a yellow transparent liquor product can be obtained. Therefore, the method utilizes MDI monomers as basic materials and abandons highly toxic TDI, toxicity of the MDI is far below TDI, and the phenol serves as blocking agent, so that the cross linking agent is fine in stability and low in unblocking temperature, and is a truly green product.
Description
Technical field
The present invention relates to a kind of preparation method of MDI-TMP.F type bridging agent.
Background technology
Bridging agent is generally that the average functional group number with NCO end group is the PU performed polymer of the low relative molecular mass of 3 left and right.By-NCO group, react with hydroxyl, carboxyl, amino groups on molecular resin chain and form crosslinkedly, can significantly improve sticking power, color stability and the resistance to retort sterilization ability etc. of polyester, Synolac and acrylic resin.Conventional bridging agent is the performed polymer of TriMethylolPropane(TMP) (TMP), 1,3-PD and 2,4-TDI (TDI 1) reaction, and TDI-TMP type bridging agent is China's turnout maximum and the most widely used bridging agent.Free carbimide TDI remaining in TDI-TMP bridging agent belongs to highly toxic substance, very large to the harm of human body, and therefore, the alternative existing TDI-TMP type bridging agent of bridging agent of seeking a kind of safety non-toxic has been imperative.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of international standard that meets is provided, low-free TDI content, the novel bridging agent of Green Product MDI-TMP.F type of safety and stability.
For achieving the above object, the preparation of the novel bridging agent of MDI-TMP.F type of the present invention is by the following technical solutions:
A preparation method for dead front type MDI-TMP.F bridging agent, comprises the following steps:
A) prepolymer reaction of MDI and TMP: first, TMP is dissolved in organic solvent ethyl acetate, adds POLYPROPYLENE GLYCOL simultaneously, prepare A liquid; Then, in reactor, add MDI, ethyl acetate and catalyzer two stannous octoates, after being uniformly mixed, in reactor, drip A liquid, the time for adding of controlling A liquid is 0.5h～5h, and the temperature of reaction kettle for reaction system is 30～120 ℃, and A drop adds after end, insulation reaction 0.5h～5h at 30～120 ℃, obtains yellow transparent liquid product MDI-TMP performed polymer;
B) capping: the phenol of metering is dissolved in ethyl acetate solvent, is added dropwise in the prepared MDI-TMP performed polymer of step a) at 40-100 ℃, drip and finish, constant temperature 0. 5h～5h, can obtain yellow transparent liquid product MDI-TMP.F type bridging agent.
As the improvement of technique scheme, mole proportioning of described MDI and TMP is 3～5.6:1.
Further such scheme is improved, the concentration of described catalyzer two stannous octoates in the prepolymer reaction system of MDI and TMP is 800～2000ppm.
Further, the mol ratio of in the active H and MDI-TMP performed polymer in described encapsulant phenol-NCO is 1.0 ~ 1.8:1.
According to above technical scheme, can realize following beneficial effect:
The present invention by experiment, has synthesized a kind of safety and stability, superior performance, and strong adhesion, color stability is good, the resistance to good novel bridging agent MDI-TMP.F of friction washing fastness that dyes of pigment.It take pure MDI monomer is basic material, abandoned highly toxic product TDI, and MDI toxicity is far below TDI, utilizes phenol as end-capping reagent, makes the product stability can be good, and deblocking temperature is low, is a kind of Green Product truly.
Embodiment
Below in conjunction with embodiment, the present invention is done further and described in detail, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1:
Clean, be dried and be equipped with in the reactor of condenser, add TMP(0.88kmol), POLYPROPYLENE GLYCOL (0.12kmol) and ethyl acetate (85.00kg) solvent, be warming up to 40 ℃-50 ℃, stirred solution TMP, after TMP dissolves completely, stop stirring, 40 ℃-50 ℃ of system temperature maintenances are stand-by.
In clean dry reactor, condenser is installed, and vacuumatic measuring adds MDI(3.20kmol), ethyl acetate (257.00kg) and catalyzer two stannous octoate 1.60kg, after shut the large lid of hand-hole, start and stir and be slowly warming up to 60 ℃. under the condition of 60 ℃ of temperature, slowly drip TMP mixing solutions, dropping temperature is controlled at 60 ℃-65 ℃, and time for adding is controlled at 2h-2.5h, after dropping finishes, at 65 ℃-70 ℃ reaction 1h, constant temperature, obtains transparent liquid MDI-TMP performed polymer.
By in active H and MDI-TMP performed polymer in encapsulant phenol-NCO takes phenol with 1.25 equivalent proportionings, be dissolved in ethyl acetate solvent, be mixed with 75% solution, proceed to feed hopper, 70 ℃ of left and right, be added dropwise in above-mentioned reaction solution, drip and finish, constant temperature 0. 5h～5h, obtain light yellow transparent liquid product MDI-TMP.F type bridging agent, solids content 74.43%, viscosity >=1500mPa.s, free TDI 0.02%.
Embodiment 2:
Clean, be dried and be equipped with in the reactor of condenser, add TMP(0.85kmol), POLYPROPYLENE GLYCOL (0.15kmol) and ethyl acetate (90.00kg) solvent, be warming up to 40 ℃-50 ℃, stirred solution TMP, after TMP dissolves completely, stop stirring, 40 ℃-50 ℃ of system temperature maintenances are stand-by.
In clean dry reactor, condenser is installed, and vacuumatic measuring adds MDI(3.20kmol), ethyl acetate (257.00kg) and catalyzer two stannous octoate 1.60kg, after shut the large lid of hand-hole, start and stir and be slowly warming up to 60 ℃. under the condition of 60 ℃ of temperature, slowly drip TMP mixing solutions, dropping temperature is controlled at 60 ℃-65 ℃, and time for adding is controlled at 2h-2.5h, after dropping finishes, at 65 ℃-70 ℃ reaction 1h, constant temperature, obtains transparent liquid MDI-TMP performed polymer.
By in active H and MDI-TMP performed polymer in encapsulant phenol-NCO takes phenol with 1.35 equivalent proportionings, be dissolved in ethyl acetate solvent, be mixed with 75% solution, proceed to feed hopper, 70 ℃ of left and right, be added dropwise in above-mentioned reaction solution, drip and finish, constant temperature 0. 5h～5h, obtain yellow transparent liquid product MDI-TMP.F type bridging agent, solids content 73.89%, viscosity >=1430mPa.s, free TDI 0.021%.
Embodiment 3:
Clean, be dried and be equipped with in the reactor of condenser, add TMP(0.88kmol), POLYPROPYLENE GLYCOL (0.12kmol) and ethyl acetate (80.00kg) solvent, be warming up to 40 ℃-50 ℃, stirred solution TMP, after TMP dissolves completely, stop stirring, 40 ℃-50 ℃ of system temperature maintenances are stand-by.
In clean dry reactor, condenser is installed, and vacuumatic measuring adds MDI(3.20kmol), ethyl acetate (257.00kg) and catalyzer two stannous octoate 1.60kg, after shut the large lid of hand-hole, start and stir and be slowly warming up to 60 ℃. under the condition of 60 ℃ of temperature, slowly drip TMP mixing solutions, dropping temperature is controlled at 60 ℃-65 ℃, and time for adding is controlled at 2h-2.5h, after dropping finishes, at 65 ℃-70 ℃ reaction 1h, constant temperature, obtains transparent liquid MDI-TMP performed polymer.
By in active H and MDI-TMP performed polymer in encapsulant phenol-NCO takes phenol with 1.35 equivalent proportionings, be dissolved in ethyl acetate solvent, be mixed with 75% solution, proceed to feed hopper, 90 ℃ of left and right, be added dropwise in above-mentioned reaction solution, drip and finish, constant temperature 2. 5h, obtain yellow transparent liquid product MDI-TMP.F type bridging agent, solids content 73.27%, viscosity >=1370mPa.s, free TDI 0.023%.
Claims (4)
1. a preparation method for dead front type MDI-TMP.F bridging agent, is characterized in that, comprises the following steps:
A) prepolymer reaction of MDI and TMP: first, TMP is dissolved in organic solvent ethyl acetate, adds POLYPROPYLENE GLYCOL simultaneously, prepare A liquid; Then, in reactor, add MDI, ethyl acetate and catalyzer two stannous octoates, after being uniformly mixed, in reactor, drip A liquid, the time for adding of controlling A liquid is 0.5h～5h, and the temperature of reaction kettle for reaction system is 30～120 ℃, and A drop adds after end, insulation reaction 0.5h～5h at 30～120 ℃, obtains yellow transparent liquid product MDI-TMP performed polymer;
B) capping: the phenol of metering is dissolved in ethyl acetate solvent, is added dropwise in the prepared MDI-TMP performed polymer of step a) at 40-100 ℃, drip and finish, constant temperature 0. 5h～5h, can obtain yellow transparent liquid product MDI-TMP.F type bridging agent.
2. the preparation method of dead front type MDI-TMP.F bridging agent according to claim 1, is characterized in that: mole proportioning of MDI and TMP is 3～5.6:1.
3. the preparation method of dead front type MDI-TMP.F bridging agent according to claim 1, is characterized in that: the concentration of catalyzer two stannous octoates in the prepolymer reaction system of MDI and TMP is 800～2000ppm.
4. the preparation method of dead front type MDI-TMP.F bridging agent according to claim 1, is characterized in that: in active H and MDI-TMP performed polymer in encapsulant phenol-and the mol ratio of NCO is 1.0 ~ 1.8:1.
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| CN201110338550.0A CN102492115B (en) | 2011-11-01 | 2011-11-01 | Preparation method for blocked MDI (diphenylmethane diisocyanate)-TMP (trimethylolpropane).F cross linking agent |
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| CN201110338550.0A CN102492115B (en) | 2011-11-01 | 2011-11-01 | Preparation method for blocked MDI (diphenylmethane diisocyanate)-TMP (trimethylolpropane).F cross linking agent |
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| CN102492115A CN102492115A (en) | 2012-06-13 |
| CN102492115B true CN102492115B (en) | 2014-02-12 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4456742A (en) * | 1983-03-17 | 1984-06-26 | Fmc Corporation | Polyurethane coating composition with a curative containing polyhydroxyalkylphosphine oxide |
| EP0505986A3 (en) * | 1991-03-25 | 1993-01-13 | Sunstar Engineering Inc. | Solvent-type 2-part adhesive and its main composition |
| CN101307127A (en) * | 2008-07-16 | 2008-11-19 | 武汉仕全兴装饰涂料有限公司 | Polyurethane curing agent with low free MDI monomer and method for preparing same |
| CN101544742A (en) * | 2009-04-15 | 2009-09-30 | 北京科聚化工新材料有限公司 | Partially blocked polyurethane curing agent and preparation method thereof |
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2011
- 2011-11-01 CN CN201110338550.0A patent/CN102492115B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4456742A (en) * | 1983-03-17 | 1984-06-26 | Fmc Corporation | Polyurethane coating composition with a curative containing polyhydroxyalkylphosphine oxide |
| EP0505986A3 (en) * | 1991-03-25 | 1993-01-13 | Sunstar Engineering Inc. | Solvent-type 2-part adhesive and its main composition |
| CN101307127A (en) * | 2008-07-16 | 2008-11-19 | 武汉仕全兴装饰涂料有限公司 | Polyurethane curing agent with low free MDI monomer and method for preparing same |
| CN101544742A (en) * | 2009-04-15 | 2009-09-30 | 北京科聚化工新材料有限公司 | Partially blocked polyurethane curing agent and preparation method thereof |
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