CN108948319A - The cold-resistant Niu Bage polyurethane resin and preparation method thereof of hydrolysis - Google Patents
The cold-resistant Niu Bage polyurethane resin and preparation method thereof of hydrolysis Download PDFInfo
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/28—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
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- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- 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
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- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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Abstract
The invention discloses the Niu Bage polyurethane resins and preparation method thereof that a kind of hydrolysis resists cold, including following component: polyester diol 1#6.5%-14%, polyester diol 2#0.1%-5%, polytetrahydrofuran ether 5%-13.5%, chain extender 0.5%-5%, methyl diphenylene diisocyanate 7%-15%, solvent 50%-75%.The present invention has many advantages, such as that anti-hydrolytic performance and cold tolerance are high using reactants and preparation method, ox Ba Ge obtained such as a variety of polyester diols, chain extender, solvents.
Description
Technical field
The present invention relates to the Niu Bage polyurethane resins and preparation method thereof that a kind of hydrolysis resists cold.
Background technique
Niu Bage, also known as " frosted skin " or " Glove suede ", its main feature is that polyurethane resin is netted in non-woven fabrics or woven fabric
The continuity elastomer for containing countless upright abscesses is formed in structure, then surface dense layer is ground off and post-processed, and makes to remove from office surface
It is evenly distributed with one layer, the down of the plentiful exquisiteness of sense of touch, to make to remove from office the good characteristic that product has natural leather, gloss
It is soft, the advantages that soft, high resilience, penetrability is good, it is mainly used as producing high-grade sport footwear, sneakers, dress shoes
Fabric and the covering materials such as wall, door and window, sofa, automobile, aviation.
A kind of water-fast degrading film Niu Bage polyurethane resin is for another example disclosed in Chinese patent literature CN104277202B
And preparation method, use wet process to manufacture, and adipic acid, butanediol and phthalic anhydride synthesize polyester diol with neopentyl glycol with non-
Often more ester bond, and the hydrolytic resistance of ester bond is poor, even if still being promoted not plus its hydrolysis effect of polyoxypropyleneglycol
Height, meanwhile, severe cold areas can not be suitable for.
Summary of the invention
To overcome disadvantages mentioned above, one of the objects of the present invention is to provide the Niu Bage polyurethane that a kind of hydrolysis resists cold
Resin.The second object of the present invention is to provide a kind of Niu Bage polyurethane that hydrolysis corresponding with the first purpose is cold-resistant
The preparation method of resin.
One of in order to reach the goals above, the technical solution adopted by the present invention is that: a kind of Niu Bage use that hydrolysis is cold-resistant
Polyurethane resin, weight percent note, including following component:
The polyester diol 1# is the reactant of adipic acid, 1,4-butanediol and hexylene glycol, the polyester diol 2#
For the reactant of adipic acid and 1,4-butanediol.
Preferably, the number-average molecular weight of the polyester diol 1# is 1500-3000.
Preferably, the number-average molecular weight of the polyester diol 2# is 300-1500.
Preferably, the polytetrahydrofuran ether includes polytetrahydrofuran ether 1#, number that number-average molecular weight is 1200-2500 equal
Molecular weight is the polytetrahydrofuran ether 2# of 2200-3800, the molar ratio of the polytetrahydrofuran ether 1# and polytetrahydrofuran ether 2#
For 0.3125-2.
Preferably, the chain extender is ethylene glycol.
Preferably, the solvent is dimethylformamide.
It preferably, further include auxiliary agent, the auxiliary agent is at least one of cell modifiers or antioxidant.
Preferably, the cell modifiers are polypropylene glycol；The antioxidant be Sminox5313, CHINOX35 or
At least one of CHINOX 510.
In order to reach the goals above two, the technical solution adopted by the present invention is that:
A kind of preparation method for the Niu Bage polyurethane resin that hydrolysis is cold-resistant, includes the following steps:
Step 1: reaction kettle is added in polyester diol 1#, polyester diol 2#, polytetrahydrofuran ether and partial solvent
It is interior, it is warming up to 50-60 DEG C, part methyl diphenylene diisocyanate is put under stirring, in 70.1-74.9 DEG C of reaction
At a temperature of react 1.0-1.9 hours, sampling viscosimetric be 13-15cps/70 DEG C, obtain performed polymer A；
The partial solvent is the 10%-20% of solvent total content, and the part methyl diphenylene diisocyanate is two
The 15%-25% of methylenebis phenyl isocyanate total content；
Step 2: chain extender and partial solvent are added in performed polymer A, it is stirred to react 10-50 minutes, part hexichol is added
Dicyclohexylmethane diisocyanate is reacted, and is reacted 1.1-1.9 hours under 70.1-74.9 DEG C of reaction temperature, is obtained performed polymer
B；
The partial solvent is the 20%-40% of solvent total content, and the part methyl diphenylene diisocyanate is two
The 60%-74% of methylenebis phenyl isocyanate total content；
Step 3: C parts of solvents are added in performed polymer B, stirring continuously added remaining diphenyl methane after 3-17 minutes
Diisocyanate slowly promotes viscosity, promotes situation according to viscosity and D parts of solvents are added, sampling viscosimetric is 130000-
Auxiliary agent and remaining solvent, stirring is added in 150000cps/70 DEG C and isocyano (NCO) content when being less than 0.001mmol/g
It is filtered and packaged after 0.5-2 hours；
The C parts of solvent is the 2%-10% of solvent total content, and the D parts of solvent is the 35%-48% of solvent total content.
Preferably, remaining diphenylmethane diisocyanate is continuously added after stirring 3-17 minutes in the step third step
Ester slowly promotes viscosity, promotes the step of D parts of solvents are added in situation according to viscosity are as follows:
(1) it is a parts into first segment solvent is added when viscosity reaches 150cps/70 DEG C, continues to add a ' part diphenylmethyl
Alkane diisocyanate promotes viscosity；
It (2) is b parts when viscosity reaches 170cps/70 DEG C or so into second segment solvent is added again, b ' part diphenyl again
Methane diisocyanate promotes viscosity, a ' part methyl diphenylene diisocyanate and b ' part methyl diphenylene diisocyanate
The sum of be remaining methyl diphenylene diisocyanate amount；
It (3) is c parts when viscosity reaches 170cps/70 DEG C or so into third section solvent is added, a parts of solvent, b parts of solvents
It is the amount of D parts of solvents with the sum of c parts of solvents；
The a parts of solvent is the 20%-35% of D parts of solvent contents；The b parts of solvent is the 20%- of D parts of solvent contents
35%；A ' part methyl diphenylene diisocyanate is the 25%-50% of remaining methyl diphenylene diisocyanate content.
Using technical solution of the present invention, when which is used to manufacture Niu Bage, inventor has surprisingly observed that
Its hydrolysis and cold tolerance have obtained significant raising, and peel load decaying is preferably 2.9%, than the prior art
4.3% improves 32.5%, achieves preferable technical effect.
Specific embodiment
The preferred embodiments of the present invention will be described in detail below so that advantages and features of the invention can be easier to by
It will be appreciated by those skilled in the art that so as to make a clearer definition of the protection scope of the present invention.
Adipic acid as described below, 1,4-butanediol, hexylene glycol, polytetrahydrofuran ether, methyl diphenylene diisocyanate, two
Methylformamide and methanol are commercially available in the market.
The polyester diol 1# is that adipic acid, 1,4-butanediol and hexylene glycol and catalyst are made, and preparation method is normal
Rule, it repeats no more；The polyester diol 2# is that adipic acid and 1,4-butanediol and catalyst are made, and preparation method is conventional
, it repeats no more.
The antioxidant that the following trade mark is Sminox5313 is selected from this Renhua work of Shanghai.
The following trade mark is CHINOX 35, the antioxidant of CHINOX 510 is selected from double bond chemical industry.
[embodiment 1]:
Step 1: by 650kg polyester diol 1#, 10kg polyester diol 2#, 381kg polytetrahydrofuran ether 1#, 119kg
Polytetrahydrofuran ether 2#, 1kgSminox5313 and 1215kg dimethylformamide is added in reaction kettle, is warming up to 55 DEG C, is stirring
Investment 170kg methyl diphenylene diisocyanate under state is mixed, is reacted 1.5 hours under 72 DEG C of reaction temperature, sampling is surveyed viscous
Degree is 14cps/70 DEG C, obtains performed polymer A；
Step 2: 50kg1.4- butanediol and 2424kg dimethylformamide are added in performed polymer A, it is stirred to react 30 points
Clock is added 462kg methyl diphenylene diisocyanate and is reacted, reacts 1.5 hours, obtain pre- under 72 DEG C of reaction temperature
Aggressiveness B；
Step 3: 566kg dimethylformamide is added in performed polymer B, stirring continuously adds remaining two after ten minutes
Methylenebis phenyl isocyanate slowly promotes viscosity, promotes situation according to viscosity and 1631kg dimethylformamide is added, sampling is surveyed
Remaining dimethyl formyl is added when viscosity is 140000cps/70 DEG C and isocyano (NCO) content is less than 0.001mmol/g
Amine, stirring filter and package after 0.5-2 hours.
[embodiment 2]:
Step 1: by 800kg polyester diol 1#, 150kg polyester diol 2#, 400kg polytetrahydrofuran ether 1#,
400kg polytetrahydrofuran ether 2#, 1kgCHINOX 35 and 1102.5kg dimethylformamide are added in reaction kettle, are warming up to 55
DEG C, 192kg methyl diphenylene diisocyanate is put under stirring, is reacted 1.5 hours, is taken under 72 DEG C of reaction temperature
Sample viscosimetric is 14cps/70 DEG C, obtains performed polymer A；
Step 2: 160kg1.4- butanediol and 2205kg dimethylformamide are added in performed polymer A, it is stirred to react 30
Minute, 528kg methyl diphenylene diisocyanate is added and is reacted, reacts 1.5 hours, obtains under 72 DEG C of reaction temperature
Performed polymer B；
Step 3: 56kg dimethylformamide is added in performed polymer B, stirring continuously adds remaining hexichol after ten minutes
Dicyclohexylmethane diisocyanate slowly promotes viscosity, promotes situation according to viscosity and 3087kg dimethylformamide is added, sampling is surveyed viscous
Remaining dimethylformamide is added for 140000cps/70 DEG C and when isocyano (NCO) content is less than 0.001mmol/g in degree,
Stirring filters and packages after 0.5-2 hours.
[embodiment 3]:
Step 1: by 900kg polyester diol 1#, 400kg polyester diol 2#, 750kg polytetrahydrofuran ether 1#,
450kg polytetrahydrofuran ether 2#, 1kgCHINOX 510 and 982.5kg dimethylformamide are added in reaction kettle, are warming up to 55
DEG C, 216kg methyl diphenylene diisocyanate is put under stirring, is reacted 1.5 hours, is taken under 72 DEG C of reaction temperature
Sample viscosimetric is 14cps/70 DEG C, obtains performed polymer A；
Step 2: 150kg1.4- butanediol and 1965kg dimethylformamide are added in performed polymer A, it is stirred to react 30
Minute, 594kg methyl diphenylene diisocyanate is added and is reacted, reacts 1.5 hours, obtains under 72 DEG C of reaction temperature
Performed polymer B；
Step 3: 458.5kg dimethylformamide is added in performed polymer B, stirring continuously adds remaining after ten minutes
Methyl diphenylene diisocyanate slowly promotes viscosity, promotes situation according to viscosity and 2751kg dimethylformamide, sampling is added
Remaining dimethyl methyl is added when viscosimetric is 140000cps/70 DEG C and isocyano (NCO) content is less than 0.001mmol/g
Amide, stirring filter and package after 0.5-2 hours.
[embodiment 4]:
Step 1: by 1100kg polyester diol 1#, 450kg polyester diol 2#, 722kg polytetrahydrofuran ether 1#,
578kg polytetrahydrofuran ether 2# and 840kg dimethylformamide are added in reaction kettle, are warming up to 55 DEG C, throw under stirring
Enter 288kg methyl diphenylene diisocyanate, reacted 1.5 hours under 72 DEG C of reaction temperature, sampling viscosimetric is 14cps/
70 DEG C, obtain performed polymer A；
Step 2: 350kg1.4- butanediol and 1680kg dimethylformamide are added in performed polymer A, it is stirred to react 30
Minute, 792kg methyl diphenylene diisocyanate is added and is reacted, reacts 1.5 hours, obtains under 72 DEG C of reaction temperature
Performed polymer B；
Step 3: 392kg dimethylformamide is added in performed polymer B, stirring continuously adds remaining two after ten minutes
Methylenebis phenyl isocyanate slowly promotes viscosity, promotes situation according to viscosity and 2352kg dimethylformamide is added, sampling is surveyed
Remaining dimethyl formyl is added when viscosity is 140000cps/70 DEG C and isocyano (NCO) content is less than 0.001mmol/g
Amine, stirring filter and package after 0.5-2 hours.
[embodiment 5]:
Step 1: by 1400kg polyester diol 1#, 500kg polyester diol 2#, 900kg polytetrahydrofuran ether 1#,
450kg polytetrahydrofuran ether 2# and 750kg dimethylformamide are added in reaction kettle, are warming up to 55 DEG C, throw under stirring
Enter 360kg methyl diphenylene diisocyanate, reacted 1.5 hours under 72 DEG C of reaction temperature, sampling viscosimetric is 14cps/
70 DEG C, obtain performed polymer A；
Step 2: 500kg1.4- butanediol and 1500kg dimethylformamide are added in performed polymer A, it is stirred to react 30
Minute, 990kg methyl diphenylene diisocyanate is added and is reacted, reacts 1.5 hours, obtains under 72 DEG C of reaction temperature
Performed polymer B；
Step 3: 350kg dimethylformamide is added in performed polymer B, stirring continuously adds remaining two after ten minutes
Methylenebis phenyl isocyanate slowly promotes viscosity, promotes situation according to viscosity and 2100kg dimethylformamide is added, sampling is surveyed
Remaining dimethyl formyl is added when viscosity is 140000cps/70 DEG C and isocyano (NCO) content is less than 0.001mmol/g
Amine, stirring filter and package after 0.5-2 hours.
[embodiment 6]:
Step 1: by 650kg polyester diol 1#, 10kg polyester diol 2#, 381kg polytetrahydrofuran ether 1#, 119kg
Polytetrahydrofuran ether 2# and 1215kg dimethylformamide are added in reaction kettle, are warming up to 55 DEG C, put under stirring
170kg methyl diphenylene diisocyanate reacts 15 hours under 72 DEG C of reaction temperature, and sampling viscosimetric is 14cps/70
DEG C, obtain performed polymer A；
Step 2: 50kg1.4- butanediol and 2424kg dimethylformamide are added in performed polymer A, it is stirred to react 30 points
Clock is added 462kg methyl diphenylene diisocyanate and is reacted, reacts 1.5 hours, obtain pre- under 72 DEG C of reaction temperature
Aggressiveness B；
Step 3: 566kg dimethylformamide is added in performed polymer B, stirring continuously added remaining hexichol after 3 minutes
Dicyclohexylmethane diisocyanate slowly promotes viscosity, promotes situation according to viscosity and 1631kg dimethylformamide is added, sampling is surveyed viscous
Remaining dimethylformamide is added for 140000cps/70 DEG C and when isocyano (NCO) content is less than 0.001mmol/g in degree,
Stirring filters and packages after 0.5-2 hours.
Wherein, remaining methyl diphenylene diisocyanate is continuously added after stirring 3-17 minutes in the step third step
Viscosity is slowly promoted, the step of 1631kg dimethylformamide is added in situation is promoted according to viscosity are as follows:
(1) it is 385.2kg into first segment dimethylformamide is added when viscosity reaches 150cps/70 DEG C, continues to add
43.75kg methyl diphenylene diisocyanate promotes viscosity；
It (2) is 385.2kg when viscosity reaches 170cps/70 DEG C or so into second segment dimethylformamide is added again, then
Secondary 131.2kg methyl diphenylene diisocyanate promotes viscosity；
It (3) is 1155.63kg when viscosity reaches 170cps/70 DEG C or so into third section dimethylformamide is added.
[embodiment 7]:
Step 1: by 650kg polyester diol 1#, 10kg polyester diol 2#, 381kg polytetrahydrofuran ether 1#, 119kg
Polytetrahydrofuran ether 2# and 1215kg dimethylformamide are added in reaction kettle, are warming up to 55 DEG C, put under stirring
170kg methyl diphenylene diisocyanate reacts 15 hours under 72 DEG C of reaction temperature, and sampling viscosimetric is 14cps/70
DEG C, obtain performed polymer A；
Step 2: 50kg1.4- butanediol and 2424kg dimethylformamide are added in performed polymer A, it is stirred to react 30 points
Clock is added 462kg methyl diphenylene diisocyanate and is reacted, reacts 1.5 hours, obtain pre- under 72 DEG C of reaction temperature
Aggressiveness B；
Step 3: 566kg dimethylformamide is added in performed polymer B, stirring continuously adds remaining two after ten minutes
Methylenebis phenyl isocyanate slowly promotes viscosity, promotes situation according to viscosity and 1631kg dimethylformamide is added, sampling is surveyed
Remaining dimethyl formyl is added when viscosity is 140000cps/70 DEG C and isocyano (NCO) content is less than 0.001mmol/g
Amine, stirring filter and package after 0.5-2 hours.
Wherein, remaining methyl diphenylene diisocyanate is continuously added after stirring 3-17 minutes in the step third step
Viscosity is slowly promoted, the step of 1631kg dimethylformamide is added in situation is promoted according to viscosity are as follows:
(1) it is 457kg into first segment dimethylformamide is added when viscosity reaches 150cps/70 DEG C, continues to add
23.8kg methyl diphenylene diisocyanate promotes viscosity；
It (2) is 457kg when viscosity reaches 170cps/70 DEG C or so into second segment dimethylformamide is added again, again
44.2kg methyl diphenylene diisocyanate promotes viscosity；
It (3) is 717kg when viscosity reaches 170cps/70 DEG C or so into third section dimethylformamide is added.
[embodiment 8]:
Step 1: by 650kg polyester diol 1#, 10kg polyester diol 2#, 381kg polytetrahydrofuran ether 1#, 119kg
Polytetrahydrofuran ether 2# and 1215kg dimethylformamide are added in reaction kettle, are warming up to 55 DEG C, put under stirring
170kg methyl diphenylene diisocyanate reacts 15 hours under 72 DEG C of reaction temperature, and sampling viscosimetric is 14cps/70
DEG C, obtain performed polymer A；
Step 2: 50kg1.4- butanediol and 2424kg dimethylformamide are added in performed polymer A, it is stirred to react 30 points
Clock is added 462kg methyl diphenylene diisocyanate and is reacted, reacts 1.5 hours, obtain pre- under 72 DEG C of reaction temperature
Aggressiveness B；
Step 3: 566kg dimethylformamide is added in performed polymer B, stirring continuously added remaining two after 17 minutes
Methylenebis phenyl isocyanate slowly promotes viscosity, promotes situation according to viscosity and 1631kg dimethylformamide is added, sampling is surveyed
Remaining dimethyl formyl is added when viscosity is 140000cps/70 DEG C and isocyano (NCO) content is less than 0.001mmol/g
Amine, stirring filter and package after 0.5-2 hours.
Wherein, remaining methyl diphenylene diisocyanate is continuously added after stirring 3-17 minutes in the step third step
Viscosity is slowly promoted, the step of 1631kg dimethylformamide is added in situation is promoted according to viscosity are as follows:
(1) it is 407.4kg into first segment dimethylformamide is added when viscosity reaches 150cps/70 DEG C, continues to add
3.5kg methyl diphenylene diisocyanate promotes viscosity；
It (2) is 407.4kg when viscosity reaches 170cps/70 DEG C or so into second segment dimethylformamide is added again, then
Secondary 3.5kg methyl diphenylene diisocyanate promotes viscosity；
It (3) is 1164kg when viscosity reaches 170cps/70 DEG C or so into third section dimethylformamide is added.
[comparative example 1]:
Step 1: 5.3kg polyadipate phthalic anhydride is newly defended glycol esterdiol, 8kg polyadipate 1,4- fourth two
Alcohol esterdiol, 5.4kg polyoxypropyleneglycol, 0.03kg2,6- di-tert-butyl p-cresol and 10.3kg dimethylformamide are added
In reaction kettle, 55 DEG C are warming up to, puts into 2.4kg4 under stirring, 4- methyl diphenylene diisocyanate is anti-at 72 DEG C
It is reacted 15 hours at a temperature of answering, sampling viscosimetric is 14cps/70 DEG C, obtains performed polymer A；
Step 2: 2kg ethylene glycol and 20.6kg dimethylformamide are added in performed polymer A, it is stirred to react 30 minutes, adds
Enter 6.7kg methyl diphenylene diisocyanate to be reacted, is reacted 1.5 hours under 72 DEG C of reaction temperature, obtain performed polymer
B；
Step 3: 4.8kg dimethylformamide is added in performed polymer B, stirring continuously adds remaining after 3-17 minutes
Methyl diphenylene diisocyanate slowly promotes viscosity, promotes situation according to viscosity and 28.8kg dimethylformamide, sampling is added
Remaining dimethyl methyl is added when viscosimetric is 140000cps/70 DEG C and isocyano (NCO) content is less than 0.001mmol/g
Amide, stirring filter and package after 0.5-2 hours.
[comparative example 2]:
By the poly- tetrahydro of 650kg polyester diol 1#, 10kg polyester diol 2#, 381kg polytetrahydrofuran ether 1#, 119kg
Furans ether 2#, 809kg dimethylformamide and 113.9kg methyl diphenylene diisocyanate are added in reaction kettle, reaction temperature
It is 70 DEG C, reacts 1-1.5 hours, obtain performed polymer；
The dimethylformamide of 809kg is added into performed polymer A, stirs 40min, the diphenyl methane two of 30.9kg is added
Isocyanates is reacted, and reaction temperature is 70 DEG C, is reacted 1.5 hours, is obtained performed polymer；
The dimethylformamide and 50kg 1.4- butanediol of 2022.9kg are added in performed polymer, stirs 40min, is added
Remaining methyl diphenylene diisocyanate is reacted, and reaction temperature is 70 DEG C, reacts 4 hours, remaining dimethyl is added
Formamide 15min can obtain hydrolysis Niu Bage polyurethane resin.
[product testing]:
Test object: the polyurethane resin in embodiment 1-8 and comparative example 1-2
Detection method: polyurethane resin to be measured is applied in release paper, and baking oven is entered after the completion of coating, and coating is viscous on it
Compound with bottom after conjunction layer, get Niu Ba is removed from office after drying, fixed line, cooling, the sample of 30mm × 30mm is cut into, according to QB/
The regulation of method B is impregnated for 24 hours in T4671-2014, and warping strength test 8 is carried out under conditions of placing it in subzero 20 degree
Ten thousand times, observe its level of breakage.
[testing result]:
The polyurethane resin according to prepared by embodiment 1-8, comparative example 1-2 is listed in table 1 under test method
Test result:
| Sample | Hydrolysis degree | Level of breakage |
| Embodiment 1 | Peel load decaying 4.2% | It does not split |
| Embodiment 2 | Peel load decaying 3.5% | It does not split |
| Embodiment 3 | Peel load decaying 2.9% | It does not split |
| Embodiment 4 | Peel load decaying 3.6% | It does not split |
| Embodiment 5 | Peel load decaying 4.3% | It does not split |
| Embodiment 6 | Peel load decaying 4% | It does not split |
| Embodiment 7 | Peel load decaying 3.7% | It does not split |
| Embodiment 8 | Peel load decaying 3.9% | It does not split |
| Comparative example 1 | Peel load decaying 4.3% | Rupture |
| Comparative example 2 | Peel load decaying 4.4% | Rupture |
(polypropylene glycol that embodiment 3 is also added into 0.1kg in addition to the ingredient of upper table)
It is above-mentioned the experimental results showed that, embodiment 1-8 has higher hydrolysis and cold tolerance, is especially with embodiment 3
It is optimal.
The technical concepts and features of embodiment of above only to illustrate the invention, its object is to allow be familiar with technique
People understands the contents of the present invention and is implemented, and it is not intended to limit the scope of the present invention, all spiritual according to the present invention
The equivalent change or modification that essence is done, should be covered by the scope of protection of the present invention.
Claims (10)
1. a kind of cold-resistant Niu Bage polyurethane resin of hydrolysis, weight percent note, including following component:
The polyester diol 1# is the reactant of adipic acid, 1,4-butanediol and hexylene glycol, and the polyester diol 2# is oneself
The reactant of diacid and 1,4-butanediol.
2. the cold-resistant Niu Bage polyurethane resin of hydrolysis according to claim 1, it is characterised in that: the polyester two
The number-average molecular weight of first alcohol 1# is 1500-3000.
3. the cold-resistant Niu Bage polyurethane resin of hydrolysis according to claim 1, it is characterised in that: the polyester two
The number-average molecular weight of first alcohol 2# is 300-1500.
4. the cold-resistant Niu Bage polyurethane resin of hydrolysis according to claim 1, it is characterised in that: the poly- tetrahydro
Furans ether include number-average molecular weight be 1200-2500 polytetrahydrofuran ether 1#, number-average molecular weight be 2200-3800 poly- tetrahydro
The molar ratio of furans ether 2#, the polytetrahydrofuran ether 1# and polytetrahydrofuran ether 2# are 0.3125-2.
5. the cold-resistant Niu Bage polyurethane resin of hydrolysis according to claim 1, it is characterised in that: the chain extender
For ethylene glycol.
6. the cold-resistant Niu Bage polyurethane resin of hydrolysis according to claim 1, it is characterised in that: the solvent is
Dimethylformamide.
7. the cold-resistant Niu Bage polyurethane resin of hydrolysis according to claim 1, it is characterised in that: further include helping
Agent, the auxiliary agent are at least one of cell modifiers or antioxidant.
8. the cold-resistant Niu Bage polyurethane resin of hydrolysis according to claim 1, it is characterised in that: the abscess tune
Section agent is polypropylene glycol；The antioxidant is at least one of Sminox5313, CHINOX 35 or CHINOX 510.
9. the preparation method of the cold-resistant Niu Bage polyurethane resin of hydrolysis described in claim 1-8, includes the following steps:
Step 1: polyester diol 1#, polyester diol 2#, polytetrahydrofuran ether and partial solvent are added in reaction kettle, rise
Temperature puts into part methyl diphenylene diisocyanate, in 70.1-74.9 DEG C of reaction temperature to 50-60 DEG C under stirring
Lower reaction 1.0-1.9 hours, sampling viscosimetric are 13-15cps/70 DEG C, obtain performed polymer A；
The partial solvent is the 10%-20% of solvent total content, and the part methyl diphenylene diisocyanate is diphenyl
The 15%-25% of methane diisocyanate total content；
Step 2: chain extender and partial solvent are added in performed polymer A, it is stirred to react 10-50 minutes, part diphenylmethyl is added
Alkane diisocyanate is reacted, and is reacted 1.1-1.9 hours under 70.1-74.9 DEG C of reaction temperature, is obtained performed polymer B；
The partial solvent is the 20%-40% of solvent total content, and the part methyl diphenylene diisocyanate is diphenyl
The 60%-74% of methane diisocyanate total content；
Step 3: C parts of solvents are added in performed polymer B, it is different that stirring continuously added remaining diphenyl methane two after 3-17 minutes
Cyanate slowly promotes viscosity, promotes situation according to viscosity and D parts of solvents are added, sampling viscosimetric is 130000-150000cps/
Auxiliary agent and remaining solvent is added in 70 DEG C and isocyano (NCO) content when being less than 0.001mmol/g, after stirring 0.5-2 hours
It filters and packages；
The C parts of solvent is the 2%-10% of solvent total content, and the D parts of solvent is the 35%-48% of solvent total content.
10. the preparation method of the cold-resistant Niu Bage polyurethane resin of hydrolysis according to claim 9, feature exist
In: remaining methyl diphenylene diisocyanate is continuously added after stirring 3-17 minutes in the step third step and is slowly promoted glues
Degree promotes the step of D parts of solvents are added in situation according to viscosity are as follows:
(1) it is a parts into first segment solvent is added when viscosity reaches 150cps/70 DEG C, continues to add a ' part diphenyl methane two
Isocyanates promotes viscosity；
It (2) is b parts when viscosity reaches 170cps/70 DEG C or so into second segment solvent is added again, b ' part diphenyl methane again
Diisocyanate promotes viscosity, the sum of a ' part methyl diphenylene diisocyanate and b ' part methyl diphenylene diisocyanate
For the amount of remaining methyl diphenylene diisocyanate；
It (3) is c parts when viscosity reaches 170cps/70 DEG C or so into third section solvent is added, a parts of solvent, b parts of solvents and c
The sum of part solvent is the amount of D parts of solvents；
The a parts of solvent is the 20%-35% of D parts of solvent contents；The b parts of solvent is the 20%-35% of D parts of solvent contents；
A ' part methyl diphenylene diisocyanate is the 25%-50% of remaining methyl diphenylene diisocyanate content.
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