CN106317379A - Preparation method of waterborne anionic closed polyisocyanate cross-linking agent - Google Patents
Preparation method of waterborne anionic closed polyisocyanate cross-linking agent Download PDFInfo
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- CN106317379A CN106317379A CN201610678114.0A CN201610678114A CN106317379A CN 106317379 A CN106317379 A CN 106317379A CN 201610678114 A CN201610678114 A CN 201610678114A CN 106317379 A CN106317379 A CN 106317379A
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- preparation
- performed polymer
- reaction
- reactant liquor
- linking agent
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8035—Masked aromatic polyisocyanates not provided for in one single of the groups C08G18/8019 and C08G18/8029
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of a waterborne anionic closed polyisocyanate cross-linking agent. The preparation method includes the steps of preparation of a prepolymer, preparation of reaction liquid, closing work and other operation. Compared with the prior art, the synthetic process is simple and standard, the production process and the production flow are easy to grasp, the prepared product is reliable in performance and good in stability, production experience summarization and accumulation are convenient, and production raw materials are good in environmental protection performance; meanwhile, the raw material reaction efficiency and the grasping and adjusting capacity of the reaction process are effectively improved, side effects generated by the cross-linking agent and water can be relieved, the activity of the cross-linking agent can be improved, and therefore the purpose of improving the material interfacial strength is achieved.
Description
Technical field
The invention belongs to new material technology field, be specifically related to a kind of aqueous anion enclosed type polyisocyanate crosslinking agent
Preparation method.
Background technology
Exploitation and the applicating history of isocyanate technology are longer, all have extremely wide answering in multiple industry fields
With, but owing to China starts late in the development and application field of water-based isocyanate material technology, therefore cause currently being made
Water-based isocyanate manufacture of materials preparation technology all be use traditional preparation technology, although traditional preparation technology one
On the other hand aspect can meet the needs of production, and also possesses the advantages such as technology maturation, but the water produced by conventional preparation techniques
Property isocyanate material time, often there is this production technology complex, grasp difficulty relatively big and be unfavorable for the total of knowhow
Knot and accumulation, the reaction property controlled that simultaneously there is also the most raw materials is poor, and raw material reaction speed is relatively
Low, therefore have a strong impact on the steady quality of the production efficiency of isocyanate material product, cost and product, and be currently used in life
Produce and the raw material of isocyanates often exists certain toxicity, therefore bigger to human body and environment existence pollution, meanwhile,
Using isocyanate material prepared by traditional production technology in actual use, the activity of cross-linking agent is relatively low, and and water
To have side effects after contact, even result in material interface intensity time serious impaired, cause the phenomenons such as cracking, thus have a strong impact on
The stability in use of cross-linking agent, therefore for this present situation, needs to develop a kind of brand-new aqueous poly-isocyanide of anion enclosed type
Acid esters cross-linking agent preparation technology, to meet actually used needs.
Summary of the invention
The technical problem to be solved in the present invention is to provide the system of a kind of aqueous anion enclosed type polyisocyanate crosslinking agent
Preparation Method, relatively low to solve the activity of prior art existence, the problems such as practical function is the best.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows:
The preparation method of a kind of aqueous anion enclosed type polyisocyanate crosslinking agent, it comprises the steps:
(1) performed polymer is prepared: under drying nitrogen is protected, TDI and methylpropane are mixed in a solvent and reacted, reaction
Liquid is cooled to room temperature and stands, and obtains performed polymer；
(2) reactant liquor is prepared: after the performed polymer heating that will prepare in step (1), under agitation add ethylene glycol ethyl ethers
Ether reacts, and obtains reactant liquor after having reacted；
(3) closed operation: after the reactant liquor prepared in step (2) is heated and stirs insulation, at shear action
Under be added thereto to 3，5-dimethylpyrazole, standing and reacting after being cooled to room temperature, obtain the aqueous poly-isocyanide of anion enclosed type
Acid esters cross-linking agent.
In step (1), described solvent is acetone, butanone, ethyl acetate or oxolane.
In step (1), the mass ratio of TDI and methylpropane is 3～8:1.
In step (1), reaction temperature is 50～100 DEG C, and the response time is 0.5～3 hour.
During reaction, in step (1), carrying out reaction system unidirectional at the uniform velocity stirring, mixing speed is 300～800 turns/min.
In step (2), heating means for be heated to 60～100 DEG C in 1～10min by performed polymer.
In step (2), the mass ratio of the performed polymer prepared in ethylene glycol and step (1) is 1:2～5.Wherein,
When adding ethylene glycol in performed polymer, the addition speed of ethylene glycol is not more than 50cm/min.
These, it is preferred to, ethylene glycol add direction contrary with performed polymer mixing direction, and with performed polymer surface in
10 °～90 ° of angles.
In step (2), reaction temperature is for for 10～60 DEG C, and the response time is 30～90min.
Wherein, in step (2), after performed polymer heating, reaction system is always maintained at unidirectional at the uniform velocity stirring, mixing speed
Being 300～800 turns/min, reaction temperature is 10 DEG C 60 DEG C, and mixing direction is identical with step (1).
In step (3), described heating means for be heated to 40～80 DEG C in 1～5min by reactant liquor, and described stirs
The method mixing insulation at the uniform velocity stirs insulation 1～2h for keeping unidirectional, and mixing speed is 300～800 turns/min.
These, it is preferred to, mixing direction is identical with step (1).
In step (3), the volume ratio of the reactant liquor prepared in 3，5-dimethylpyrazole and step (2) is 1:8～20.
These, it is preferred to, the interpolation direction of 3，5-dimethylpyrazole is identical with performed polymer mixing direction, and and performed polymer
Surface is 10 °～90 ° of angles, and shearing force is 300N～1000N for average mixing liquid every square millimeter pressure experienced；
In step (3), reaction temperature is 40～80 DEG C, and the response time is 2～5h.
In step (1)～(3), reaction system is under the protection of drying nitrogen, and nitrogen pressure is that 1～6 standard is big
Air pressure.
Beneficial effect:
Compared with prior art, the present invention has the advantage that
Synthesis technique simple specification of the present invention, production technology and production procedure are easily grasped, and the properties of product of preparation are reliable
Good stability, it is simple to knowhow is summed up and accumulation, and raw materials for production good environmental protection, meanwhile the most effective raising
Raw material reaction efficiency and the control regulating power to course of reaction, thus contribute to improving cross-linking agent and have side effects with water and carry
The activity of high cross-linking agent, thus reach to improve the purpose of material interface intensity.
Accompanying drawing explanation
Fig. 1 is present invention process flow chart..
Detailed description of the invention
According to following embodiment, the present invention be may be better understood.But, as it will be easily appreciated by one skilled in the art that reality
Execute the content described by example and be merely to illustrate the present invention, and should be also without limitation on basis described in detail in claims
Invention.
Embodiment 1
Aqueous anion enclosed type polyisocyanate crosslinking agent preparation technology as shown in Figure 1, comprises the following steps；
The first step, prepares performed polymer, is under 80 DEG C of environment in drying nitrogen protection and temperature, by TDI and trihydroxy methyl third
Alkane carries out mixing by acetone and fully reacts 1.5 hours, and in carrying out mixing and course of reaction, mixture is carried out up time
Pin direction is at the uniform velocity stirred, and mixing speed is 500 turns per minute, after completing reaction, mixture temperature is naturally cooled to room temperature also
Standing and obtain performed polymer in 15 minutes, wherein the weight ratio of TDI and methylpropane is 5:1；
Second step, prepares reactant liquor, and the performed polymer first step prepared was heated to 60 DEG C in 3 minutes, then to pre-polymerization
Body is carried out and the first step at the uniform velocity stirring operation in the same direction, and mixing speed is 800 turns per minute, treats that performed polymer mixing speed is stable
After, add ethylene glycol to performed polymer and fully react, when wherein ethylene glycol adds, speed is 30 centimetres of speed per minute
Degree, and ethylene glycol interpolation direction is contrary with performed polymer mixing direction, and be 15 ° of angles with performed polymer surface, complete second two
After alcohol ether adds, the state that is kept stirring for mixed liquor obtains reactant liquor in 40 minutes, wherein makes in ethylene glycol and the first step
Standby mixed liquor weight ratio is 1:3；
3rd step, closed operation, the reactant liquor prepared by second step was adjusted to 40 DEG C at 3 minutes, and kept and second step
The unidirectional at the uniform velocity stirring insulation synchronized 1 hour, then adds 3 under high shear in reactant liquor prepared by second step,
5-dimethyl pyrazole, and the interpolation direction of 3，5-dimethylpyrazole is identical with reactant liquor mixing direction, mixing speed is per minute
300 turns, and be 30 ° of angles with reactant liquor liquid level, after 3，5-dimethylpyrazole adds, mixed liquor is stood insulation reaction 2 little
Time, then stop stirring and naturally cool to room temperature, wherein shearing force is that averagely mixing liquid every square millimeter is subject to
Pressure is 500N, and 3，5-dimethylpyrazole is 1:10 with the weight ratio of second step mixed liquor.
In the present embodiment, the nitrogen pressure in drying nitrogen protection in the described first step is 5 normal atmospheres, and
Nitrogen protection starts up to the 3rd EOS from the first step.
Embodiment 2
Aqueous anion enclosed type polyisocyanate crosslinking agent preparation technology as shown in Figure 1, comprises the following steps；
The first step, prepares performed polymer, is under 60 DEG C of environment in drying nitrogen protection and temperature, by TDI and trihydroxy methyl third
Alkane carries out mixing by acetone and fully reacts 1 hour, and in carrying out mixing and course of reaction, carries out mixture clockwise
Direction is at the uniform velocity stirred, and mixing speed is 400 turns per minute, and mixture temperature naturally cools to after completing reaction room temperature quiet
Putting 10 minutes and obtain performed polymer, wherein the weight ratio of TDI and methylpropane is 8:1；
Second step, prepares reactant liquor, and the performed polymer first step prepared was heated to 50 DEG C in 3 minutes, then to pre-polymerization
Body is carried out and the first step at the uniform velocity stirring operation in the same direction, and mixing speed is 500 turns per minute, treats that performed polymer mixing speed is stable
After, add ethylene glycol to performed polymer and fully react, when wherein ethylene glycol adds, speed is 40 centimetres of speed per minute
Degree, and ethylene glycol interpolation direction is contrary with performed polymer mixing direction, and be 15 ° of angles with performed polymer surface, complete second two
After alcohol ether adds, the state that is kept stirring for mixed liquor obtains reactant liquor in 30 minutes, wherein makes in ethylene glycol and the first step
Standby mixed liquor weight ratio is 1:5；
3rd step, closed operation, the reactant liquor prepared by second step was adjusted to 60 DEG C at 3 minutes, and kept and second step
The unidirectional at the uniform velocity stirring insulation synchronized 1.5 hours, then adds under high shear in reactant liquor prepared by second step
3，5-dimethylpyrazole, and the interpolation direction of 3，5-dimethylpyrazole is identical with reactant liquor mixing direction, mixing speed is every point
500 turns of clock, and be 15 ° of angles with reactant liquor liquid level, after 3，5-dimethylpyrazole adds, mixed liquor is stood insulation reaction 2
Hour, then stop stirring and naturally cool to room temperature, wherein shearing force is subject to for average mixing liquid every square millimeter
Pressure be 1000N, the weight ratio of 3，5-dimethylpyrazole and second step mixed liquor is 1:15.
In the present embodiment, the nitrogen pressure in drying nitrogen protection in the described first step is 3 normal atmospheres, and
Nitrogen protection starts up to the 3rd EOS from the first step.
Synthesis technique simple specification of the present invention, production technology and production procedure are easily grasped, and the properties of product of preparation are reliable
Good stability, it is simple to knowhow is summed up and accumulation, and raw materials for production good environmental protection, meanwhile the most effective raising
Raw material reaction efficiency and the control regulating power to course of reaction, thus contribute to improving cross-linking agent and have side effects with water and carry
The activity of high cross-linking agent, thus reach to improve the purpose of material interface intensity.
Claims (10)
1. the preparation method of an aqueous anion enclosed type polyisocyanate crosslinking agent, it is characterised in that it includes walking as follows
Rapid:
(1) preparing performed polymer: under nitrogen protection, TDI and methylpropane are mixed in a solvent and reacted, reactant liquor is cooled to
Room temperature also stands, and obtains performed polymer；
(2) prepare reactant liquor: after the performed polymer heating that will prepare in step (1), under agitation add ethylene glycol and enter
Row reaction, obtains reactant liquor after having reacted；
(3) closed operation: after the reactant liquor prepared in step (2) is heated and stirs insulation, under shear action to
Wherein add 3，5-dimethylpyrazole, standing and reacting after being cooled to room temperature, obtain aqueous anion enclosed type polyisocyanate
Cross-linking agent.
Preparation method the most according to claim 1, it is characterised in that in step (1), described solvent be acetone, butanone,
Ethyl acetate or oxolane.
Preparation method the most according to claim 1, it is characterised in that in step (1), TDI and the mass ratio of methylpropane
It is 3～8:1.
Preparation method the most according to claim 1, it is characterised in that in step (1), reaction temperature is 50～100 DEG C, instead
It is 0.5～3 hour between Ying Shi.
Preparation method the most according to claim 1, it is characterised in that during reaction, in step (1), is carried out reaction system
Unidirectional at the uniform velocity stirring, mixing speed is 300～800 turns/min.
Preparation method the most according to claim 1, it is characterised in that in step (2), heating means are in 1～10min
Performed polymer is heated to 60～100 DEG C.
In preparation method the most according to claim 1, it is characterised in that in step (2), ethylene glycol and step (1)
The mass ratio of the performed polymer prepared is 1:2～5.
Preparation method the most according to claim 1, it is characterised in that in step (2), reaction temperature for for 10～60 DEG C,
Response time is 30～90min.
Preparation method the most according to claim 1, it is characterised in that in step (3), 3，5-dimethylpyrazole and step
(2) volume ratio of the reactant liquor prepared in is 1:8～20.
Preparation method the most according to claim 1, it is characterised in that in step (3), reaction temperature is 40～80 DEG C, instead
It is 2～5h between Ying Shi.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610678114.0A CN106317379A (en) | 2016-08-16 | 2016-08-16 | Preparation method of waterborne anionic closed polyisocyanate cross-linking agent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610678114.0A CN106317379A (en) | 2016-08-16 | 2016-08-16 | Preparation method of waterborne anionic closed polyisocyanate cross-linking agent |
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| CN201610678114.0A Pending CN106317379A (en) | 2016-08-16 | 2016-08-16 | Preparation method of waterborne anionic closed polyisocyanate cross-linking agent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107236114A (en) * | 2017-06-15 | 2017-10-10 | 盐城工学院 | A kind of watersoluble closed type polyisocyanate crosslinking agent of nano-silica-containing structure and preparation method thereof |
| CN108587112A (en) * | 2018-04-13 | 2018-09-28 | 上海浩登材料股份有限公司 | A kind of aqueous aromatic polyisocyanate crosslinking agent and preparation method thereof |
Citations (3)
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| CN101948432A (en) * | 2010-08-03 | 2011-01-19 | 河南斯维科技有限公司 | 3.5-dimethyl pyrazol closed isophorone diisocyanate monomer additive product and preparation method thereof |
| CN102372833A (en) * | 2011-11-01 | 2012-03-14 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing sealed MDI-TMP.E bridging agents |
| CN104448234A (en) * | 2014-12-08 | 2015-03-25 | 盐城工学院 | Waterborne blocked hyperbranched polyisocyanate cross-linking agent and preparation method thereof |
-
2016
- 2016-08-16 CN CN201610678114.0A patent/CN106317379A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948432A (en) * | 2010-08-03 | 2011-01-19 | 河南斯维科技有限公司 | 3.5-dimethyl pyrazol closed isophorone diisocyanate monomer additive product and preparation method thereof |
| CN102372833A (en) * | 2011-11-01 | 2012-03-14 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing sealed MDI-TMP.E bridging agents |
| CN104448234A (en) * | 2014-12-08 | 2015-03-25 | 盐城工学院 | Waterborne blocked hyperbranched polyisocyanate cross-linking agent and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107236114A (en) * | 2017-06-15 | 2017-10-10 | 盐城工学院 | A kind of watersoluble closed type polyisocyanate crosslinking agent of nano-silica-containing structure and preparation method thereof |
| CN107236114B (en) * | 2017-06-15 | 2021-01-29 | 盐城工学院 | Water-based closed polyisocyanate crosslinking agent containing nano silicon dioxide structure and preparation method thereof |
| CN108587112A (en) * | 2018-04-13 | 2018-09-28 | 上海浩登材料股份有限公司 | A kind of aqueous aromatic polyisocyanate crosslinking agent and preparation method thereof |
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Application publication date: 20170111 |
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