CN106866913A - The method that one-step method prepares foaming type polyurethane resin - Google Patents
The method that one-step method prepares foaming type polyurethane resin Download PDFInfo
- Publication number
- CN106866913A CN106866913A CN201510922228.0A CN201510922228A CN106866913A CN 106866913 A CN106866913 A CN 106866913A CN 201510922228 A CN201510922228 A CN 201510922228A CN 106866913 A CN106866913 A CN 106866913A
- Authority
- CN
- China
- Prior art keywords
- glycol
- esterdiol
- molecular weight
- polyadipate
- ppg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08G18/40—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
-
- 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
- C08G18/28—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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- 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
-
- 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
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of method that one-step method prepares foaming type polyurethane resin, comprise the following steps：(1) in a solvent, isocyanates reaction will after several mixing in polyalcohol, chain extender and crosslinking agent, be added；Described polyalcohol is one kind or its combination in PEPA, PPG or PCDL；(2) it is subsequently adding C2-6Aliphatic aldoxime is closed, and obtains enclosed type performed polymer；(3) aromatic isocyanate dispersion mixing is added, blade coating is toasted on base material, you can obtain described foaming type polyurethane resin.The advantage of the invention is that：Different densities size foam films are obtained using the usage ratio of different polyester, polyethers, chain extender etc., peel strength can adjust, and the foaming early stage dispensing resting period is long, additionally, cross-linked structure foaming film properties are also more stable.
Description
Technical field
The present invention relates to a kind of preparation method of the type polyurethane resin that foams.
Technical background
Polyurethane foam resin is mainly prepared using physical blowing and Water blown two ways.Wherein physical blowing agent is deposited
Damaging the ozone layer, inflammable and explosive problem, though existing reduce into forth generation product to environmental hazard, price is high, influences city
The application prospect of field.Solvent-free double-component resin discharges CO by water with isocyanates fast reaction2Foaming is realized, but due to anti-
At once it is extremely short between, cause mixing uneven and high to equipment measuring requirement, and double-component viscosity differences are big high to mixing generation
Influence, cause the stability of product not enough.Therefore, in the urgent need to researching and developing a kind of preparation of new foaming type polyurethane resin
Method, can be dispersed for a long time with low speed, obtains more stable cross-linked structure foam films.
The content of the invention
It is an object of the invention to provide a kind of method that one-step method prepares foaming type polyurethane resin, to overcome prior art
In defect.
Preparation method of the invention, comprises the following steps：
(1) in a solvent, by after several mixing in polyalcohol, chain extender and crosslinking agent, isocyanates, 70~80 are added
DEG C, preferably 75 DEG C, 1-3h is reacted, determine whether fully to react by determining NCO；
Described polyalcohol is one kind or its combination in PEPA, PPG or PCDL；
(2) it is subsequently adding C2-6Aliphatic aldoxime is closed, 75~85 DEG C, preferably 80 DEG C 10~50min of reaction, preferably
30min, obtains enclosed type performed polymer；
(3) add aromatic isocyanate, in 400-500r/min dispersion mixing 1.5-2min, blade coating on base material in
140-160 DEG C of baking 5~20min, preferably 10min can obtain described foaming type polyurethane resin.
In above step, enclosed type performed polymer is with aromatic isocyanate mass fraction：
100 parts of enclosed type performed polymer
5~15 parts of aromatic isocyanate, preferably 5~11 parts；
In enclosed type performed polymer, the mass percent of each component is as follows：
The percentage sum of each component is 100%；
Preferably, the mass percent of each component is as follows：
The percentage sum of each component is 100%.
Described PEPA, polyester construction, molecular weight 250-10000, selected from being not limited to are contained containing 2 terminal hydroxy groups：It is poly-
NGA neopentyl glycol adipate glycol (PNA), the butyl glycol ester diol of polyadipate -1,4 (PBA), the hexylene glycol ester of polyadipate -1,6
Glycol, polyethylene glycol adipate glycol, polyadipate methyl propanediol esterdiol, polyadipate diethylene glycol (DEG) esterdiol, gather oneself
One or more in diacid butanediol methyl propanediol esterdiol.
Described PPG, ether structure is contained containing 2 or 3 terminal hydroxy groups, molecular weight 250-10000, selected from being not limited to：
Polyoxypropyleneglycol (PPG), the three-functionality-degree PPG with methyl propanediol or glycerine as initiator, polyoxyethylene glycol
(PEG), one or more in polytetramethylene ether diol (PTMEG).
Described PCDL, containing 2 terminal hydroxy group carbonate-containing structures, molecular weight 250-10000, by carbonic diester
With binary alcohol esters synthesis, selected from being not limited to：Polytetramethylene carbonate diol glycol, poly- neopentyl glycol carbonate esterdiol, poly- carbonic acid hexylene glycol
One or more in esterdiol.
Preferably：
Described polyalcohol is the polyneopentyl glycol adipate glycol and the polyoxygenated third of molecular weight 2000 of molecular weight 2000
Enediol (PPG), polyneopentyl glycol adipate glycol is 5 with polyoxypropyleneglycol weight ratio:0.8~1.2；It is preferred that 5:1；
Or：Described polyalcohol is the butyl glycol ester diol of polyadipate -1,4 of molecular weight 2000, molecular weight 2000
The polyoxypropyleneglycol of polyadipate methyl propanediol esterdiol and molecular weight 480, weight ratio is：
The butyl glycol ester diol of polyadipate -1,4：Polyadipate methyl propanediol esterdiol：Polyoxypropyleneglycol
=1:1.8~2.2~0.01~0.05, preferably 1:2:0.03；
Or：Described polyalcohol is the poly- carbonic acid hexylene glycol esterdiol of molecular weight 2000, molecular weight 2000 gathers oneself two
The polytetramethylene ether diol PTMEG of sour diethylene glycol (DEG) esterdiol and molecular weight 2000, weight ratio is：
Poly- carbonic acid hexylene glycol esterdiol：Polyadipate diethylene glycol (DEG) esterdiol：Polytetramethylene ether diol=
1:0.8~1.2:0.02~0.03, preferably 1:1:0.025；
Described chain extender is selected from ethylene glycol (EG), 1,4- butanediols (BDO), neopentyl glycol (NPG), 1,6-HD
(HDO) one or more.
Described crosslinking agent is selected from trimethylolpropane (TMP) and/or glycerine.
Described isocyanates is selected from one or more of TDI-100 (2,4 toluene diisocyanate) or MDI-50；
Described MDI-50, includes 50% 4,4- methyl diphenylene diisocyanates, 50% 2,4- diphenyl methanes
Diisocyanate；
Described aromatic isocyanate, selected from MDI-40 to MDI-100 or TDI-65 to TDI-100 it is a kind of with
On；
Described MDI-40 to MDI-100, refers to that 4,4- methyl diphenylene diisocyanates and 2,4- diphenyl methane two are different
The mass ratio of cyanate is from 40:60 to 100:0；
Described TDI-65 to TDI-100, nail benzene 2,4- diisocyanate and toluene 2, the quality of 6- diisocyanate
Than from 65:35 to 100:0；
Preferably, C2-6Aliphatic aldoxime is selected from acetaldoxime, propionaldoxime, butyl aldoxime or the first and second aldoximes；
Described solvent is selected from N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAC), propyl acetate
(PAc), butyl acetate (BuAc), toluene (TOL) or propylene glycol methyl ether acetate (PMA).
Term " molecular weight " refers to number-average molecular weight.
The advantage of the invention is that：Design the usage ratio of different polyester, polyethers, chain extender etc. big to obtain different densities
Small foam films, peel strength can adjust, and the foaming early stage dispensing resting period is long, additionally, cross-linked structure foaming film properties are also more steady
It is fixed.
Specific embodiment
By specific examples below, the present invention is described in detail, but the scope that the present invention is protected is not limited to this
A little embodiments, the formula of the also non-intrinsically safe including being done according to the content of the invention is adjusted and process modifications.
The raw material explanation for being used
PEPA：
polyol1：Polyneopentyl glycol adipate glycol (PNA), molecular weight 2000, degree of functionality 2；
polyol3：Polyadipate-Isosorbide-5-Nitrae butyl glycol ester diol (PBA), molecular weight 2000, degree of functionality 2；
polyol4：Polyadipate methyl propanediol esterdiol, molecular weight 2000, degree of functionality 2；
polyol6：Polybutyleneadipate methyl propanediol esterdiol, molecular weight 2000, degree of functionality 2；
polyol8：Polyadipate diethylene glycol (DEG) esterdiol, molecular weight 2000, degree of functionality 2；
PPG：
polyol2：Polyoxypropyleneglycol (PPG), molecular weight 2000, degree of functionality 2；
polyol5：Polyoxypropyleneglycol (PPG), molecular weight 480, crosslinking agent is methyl propanediol or glycerine, degree of functionality
3；
polyol9：Polytetramethylene ether diol PTMEG, molecular weight 2000, degree of functionality 2；
PCDL：
polyol7：Poly- carbonic acid hexylene glycol esterdiol, molecular weight 2000, degree of functionality 2；
TMP：Trimethylolpropane
EG：Ethylene glycol
BDO：1,4- butanediols
TDI-100：2,4 toluene diisocyanate
TDI-65：Include 65%2,4- toluene di-isocyanate(TDI)s, 35%2,6- toluene di-isocyanate(TDI)s
MDI-100：4,4- methyl diphenylene diisocyanates
MDI-50：Include 50% 4,4- methyl diphenylene diisocyanates and 50% isocyanide of 2,4- diphenyl methanes two
Acid esters
DMF：N,N-dimethylformamide
PMA：Propylene glycol methyl ether acetate
BuAc：Butyl acetate
TOL：Toluene
Embodiment 1
Polyol1, polyol2, TMP, EG, DMF are added in 1L reaction bulbs, after 35 DEG C of mixing 20min, TDI- is added
100,75 DEG C of reaction 2h are warming up to, it is 3.5% to determine NCO, and acetaldoxime is added after being cooled to 65 DEG C, treats temperature stabilization after 80 DEG C
Insulation reaction 30min, is obtained 85% solid content resin.
The resin 100g after synthesis is taken, the MDI-100 of the 10.6g after being diluted through 30g DMF is added, is opened and dispersion impeller is housed
Mixer 500rpm dispersion 2min, stabilization time be up to 20min, with 30s scrapers scratch on base material 160 DEG C baking
10min, you can obtain described foaming type polyurethane resin, cell diameter is 190 μm, and test peel strength reaches 105N/m.
The resin 100g after synthesis is taken, after adding the MDI-50 of 10.6g, mixer 500rpm points equipped with dispersion impeller is opened
2min is dissipated, stabilization time is up to 30min, scratched in toasting 10min at 140 DEG C on base material with 30s scrapers, you can obtain described
Foaming type polyurethane resin, cell diameter is 144 μm, and test peel strength reaches 121N/m.
Embodiment 2
Polyol3, polyol4, polyol5, DMF and BuAc are added in 1L reaction bulbs, after 35 DEG C of mixing 20min, plus
Enter MDI-50, be warming up to 75 DEG C of reaction 2h, it is 2.5% to determine NCO, acetaldoxime is added after being cooled to 65 DEG C, after after temperature stabilization
In 80 DEG C of insulation reaction 30min, 80% solid content resin is obtained.
The resin 100g after synthesis is taken, after adding the TDI-100 of 5.39g, the mixer 400rpm equipped with dispersion impeller is opened
Dispersion 2min, stabilization time is up to 10min, is scratched in toasting 10min at 160 DEG C on base material with 30s scrapers, you can obtain described
Foaming type polyurethane resin, cell diameter be 195 μm, test peel strength reach 106N/m.
The resin 100g after synthesis is taken, after adding the TDI-65 of 5.39g, mixer 400rpm points equipped with dispersion impeller is opened
2min is dissipated, stabilization time is up to 10min, scratched in toasting 10min at 140 DEG C on base material with 30s scrapers, you can obtain described
Foaming type polyurethane resin, cell diameter is 240 μm, and test peel strength reaches 80N/m.
Embodiment 3
Polyol6, TMP, DMF are added in 1L reaction bulbs, after 35 DEG C of mixing 20min, MDI-50 is added, 75 DEG C are warming up to
Reaction 1h, it is 2.32% to determine NCO, and butyl aldoxime is added after being cooled to 65 DEG C, treats temperature stabilization after 80 DEG C of insulation reactions
30min, is obtained 80% solid content resin.
The resin 100g after synthesis is taken, after adding the MDI-50 of 8.59g, mixer 400rpm points equipped with dispersion impeller is opened
Dissipate 2min, stabilization time be up to 60min, with 30s scrapers scratch on base material 140-160 DEG C toast 10min, you can obtain institute
The foaming type polyurethane resin stated, cell diameter is 239 μm, and test peel strength reaches 106N/m.
Embodiment 4
Polyol6, TMP, BDO, PMA are added in 1L reaction bulbs, after 35 DEG C of mixing 20min, MDI-50 is added, is warming up to
75 DEG C of reaction 1.5h, it is 2.9% to determine NCO, and acetaldoxime is added after being cooled to 60 DEG C, treats temperature stabilization after 80 DEG C of insulation reactions
30min, is obtained 80% solid content resin.
The resin 100g after synthesis is taken, after adding the MDI-50 of 7.76g, mixer 400rpm points equipped with dispersion impeller is opened
Dissipate 2min, stabilization time be up to 20min, with 30s scrapers scratch on base material 140-160 DEG C toast 10min, you can obtain institute
The foaming type polyurethane resin stated, cell diameter is 311 μm, and test peel strength is 40N/m.
Embodiment 5
Polyol7, polyol8, polyol9, TMP, PMA and TOL are added in 1L reaction bulbs, 20min is mixed in 35 DEG C
Afterwards, MDI-50 is added, 75 DEG C of reaction 2h are warming up to, it is 2.65% to determine NCO, and butyl aldoxime is added after being cooled to 65 DEG C, treats temperature
Stabilization is obtained 70% solid content resin after 80 DEG C of insulation reaction 30min.
The resin 100g after synthesis is taken, after adding the MDI-40 of 8.51g, mixer 400rpm points equipped with dispersion impeller is opened
1.5min is dissipated, stabilization time is up to 30min, scratched in toasting 10min at 150 DEG C on base material with 30s scrapers, you can obtain described
Foaming type polyurethane resin, cell diameter be 460 μm, test peel strength be 80N/m.
Claims (9)
1. the method that one-step method prepares foaming type polyurethane resin, it is characterised in that comprise the following steps：
(1) in a solvent, isocyanates reaction will after several mixing in polyalcohol, chain extender and crosslinking agent, be added；
Described polyalcohol is one kind or its combination in PEPA, PPG or PCDL；
(2) it is subsequently adding C2-6Aliphatic aldoxime is closed, and obtains enclosed type performed polymer；
(3) aromatic isocyanate dispersion mixing is added, blade coating is toasted on base material, you can obtain described foaming type polyurethane
Resin.
2. method according to claim 1, it is characterised in that (1) in a solvent, by polyalcohol, chain extender and crosslinking agent
In several mixing after, add isocyanates, 70~80 DEG C, react 1-3h；
Described polyalcohol is one kind or its combination in PEPA, PPG or PCDL；
(2) it is subsequently adding C2-6Aliphatic aldoxime is closed, 75~85 DEG C, reacts 10~50min, obtains enclosed type performed polymer；
(3) aromatic isocyanate is added, in 400-500r/min dispersion mixing 1.5-2min, blade coating is on base material in 140-
160 DEG C of 5~20min of baking can obtain described foaming type polyurethane resin Foamex.
3. method according to claim 1, it is characterised in that enclosed type performed polymer and aromatic isocyanate mass fraction
For：
100 parts of enclosed type performed polymer
5~15 parts of aromatic isocyanate.
4. envelope method according to claim 1, it is characterised in that in enclosed type performed polymer, the mass percent of each component
It is as follows：
The percentage sum of each component is 100%.
5. method according to claim 1, it is characterised in that in enclosed type performed polymer, the mass percent of each component is such as
Under：
The percentage sum of each component is 100%.
6. the method according to any one of Claims 1 to 5, it is characterised in that described PEPA, molecular weight 250-
10000；Described PPG, ether structure, molecular weight 250-10000 are contained containing 2 or 3 terminal hydroxy groups；Described poly- carbonic acid
Esterdiol, molecular weight 250-10000.
7. method according to claim 6, it is characterised in that described PEPA is selected from and is not limited to：Polyadipate
It is neopentyl glycol esterdiol (PNA), the butyl glycol ester diol of polyadipate -1,4 (PBA), the hexylene glycol of polyadipate -1,6 esterdiol, poly-
Ethylene glycol adipate glycol, polyadipate methyl propanediol esterdiol, polyadipate diethylene glycol (DEG) esterdiol, polyadipate fourth two
One or more in alcohol methyl propanediol esterdiol；
Described PPG, selected from being not limited to：Polyoxypropyleneglycol (PPG), it is starting with methyl propanediol or glycerine
One or more in three-functionality-degree PPG, polyoxyethylene glycol (PEG), the polytetramethylene ether diol (PTMEG) of agent；
Described PCDL, selected from being not limited to：Polytetramethylene carbonate diol glycol, poly- neopentyl glycol carbonate esterdiol, poly- carbonic acid oneself
One or more in glycol esterdiol.
8. method according to claim 7, it is characterised in that described polyalcohol is new for the polyadipate of molecular weight 2000
Pentadiol ester glycol and the polyoxypropyleneglycol of molecular weight 2000 (PPG), polyneopentyl glycol adipate glycol and polyoxygenated third
Enediol weight ratio is 5:0.8~1.2；
Or：Described polyalcohol is the butyl glycol ester diol of polyadipate -1,4 of molecular weight 2000, molecular weight 2000 gathers oneself
The polyoxypropyleneglycol of diacid methyl propanediol esterdiol and molecular weight 480, weight ratio is：
The butyl glycol ester diol of polyadipate -1,4：Polyadipate methyl propanediol esterdiol：Polyoxypropyleneglycol=1:1.8~
2.2~0.01~0.05；
Or：Described polyalcohol is poly- carbonic acid hexylene glycol esterdiol, the polyadipate two of molecular weight 2000 of molecular weight 2000
The polytetramethylene ether diol PTMEG of glycol esterdiol and molecular weight 2000, weight ratio is：Poly- carbonic acid hexylene glycol esterdiol：It is poly-
Diethylene glycol adipate glycol：Polytetramethylene ether diol=1:0.8~1.2:0.02~0.03.
9. the method according to any one of Claims 1 to 5, it is characterised in that described chain extender be selected from ethylene glycol (EG),
One or more of 1,4- butanediols (BDO), neopentyl glycol (NPG), 1,6-HD (HDO)；
Described crosslinking agent is selected from trimethylolpropane (TMP) and/or glycerine；
Described isocyanates is selected from one or more of TDI-100 (2,4 toluene diisocyanate) or MDI-50；
Described MDI-50, includes 50% 4,4- methyl diphenylene diisocyanates, and 50% 2,4- diphenyl methanes two are different
Cyanate；
Described aromatic isocyanate, selected from one or more of MDI-40 to MDI-100 or TDI-65 to TDI-100；
Described MDI-40 to MDI-100, refers to 4,4- methyl diphenylene diisocyanates and 2,4- diphenylmethane diisocyanate
The mass ratio of ester is from 40:60 to 100:0；
Described TDI-65 to TDI-100, nail benzene 2,4- diisocyanate and toluene 2, the mass ratio of 6- diisocyanate from
65:35 to 100:0；
C2-6Aliphatic aldoxime is selected from acetaldoxime, propionaldoxime, butyl aldoxime or the first and second aldoximes；
The solvent is selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, propyl acetate, butyl acetate, toluene or third
Glycol methyl ether acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510922228.0A CN106866913B (en) | 2015-12-11 | 2015-12-11 | Method for preparing foaming polyurethane resin by one-step method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510922228.0A CN106866913B (en) | 2015-12-11 | 2015-12-11 | Method for preparing foaming polyurethane resin by one-step method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106866913A true CN106866913A (en) | 2017-06-20 |
| CN106866913B CN106866913B (en) | 2019-12-20 |
Family
ID=59177647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510922228.0A Active CN106866913B (en) | 2015-12-11 | 2015-12-11 | Method for preparing foaming polyurethane resin by one-step method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106866913B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109337035A (en) * | 2018-10-10 | 2019-02-15 | 江苏华峰超纤材料有限公司 | High resistance to toluene polyurethane resin for superfine fiber synthetic leather and preparation method thereof |
| CN116375970A (en) * | 2023-03-01 | 2023-07-04 | 中山博锐斯新材料股份有限公司 | Ultra-high water absorption TPU material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4442259A (en) * | 1982-04-26 | 1984-04-10 | W. R. Grace & Co. | Aqueous-based polyurethane compositions and method of preparation |
| JPH0625597A (en) * | 1992-07-07 | 1994-02-01 | Toyota Motor Corp | Interlaminar chipping-resistant paint for automobile |
| WO2004096884A1 (en) * | 2003-05-02 | 2004-11-11 | Bridgestone Corporation | Crosslinkable polyurethane compositions |
| CN101580578A (en) * | 2009-04-15 | 2009-11-18 | 浙江华峰合成树脂有限公司 | High solid foaming polyurethane resin for synthetic leather and preparing method thereof |
| CN103772647A (en) * | 2012-10-18 | 2014-05-07 | 襄阳精信汇明化工有限责任公司 | Closed diphenyl-methane-diisocyanate curing agent and preparation method thereof |
-
2015
- 2015-12-11 CN CN201510922228.0A patent/CN106866913B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4442259A (en) * | 1982-04-26 | 1984-04-10 | W. R. Grace & Co. | Aqueous-based polyurethane compositions and method of preparation |
| JPH0625597A (en) * | 1992-07-07 | 1994-02-01 | Toyota Motor Corp | Interlaminar chipping-resistant paint for automobile |
| WO2004096884A1 (en) * | 2003-05-02 | 2004-11-11 | Bridgestone Corporation | Crosslinkable polyurethane compositions |
| CN101580578A (en) * | 2009-04-15 | 2009-11-18 | 浙江华峰合成树脂有限公司 | High solid foaming polyurethane resin for synthetic leather and preparing method thereof |
| CN103772647A (en) * | 2012-10-18 | 2014-05-07 | 襄阳精信汇明化工有限责任公司 | Closed diphenyl-methane-diisocyanate curing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 彭安顺等主编: "《精细有机品化学》", 31 August 1996, 石油大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109337035A (en) * | 2018-10-10 | 2019-02-15 | 江苏华峰超纤材料有限公司 | High resistance to toluene polyurethane resin for superfine fiber synthetic leather and preparation method thereof |
| CN116375970A (en) * | 2023-03-01 | 2023-07-04 | 中山博锐斯新材料股份有限公司 | Ultra-high water absorption TPU material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106866913B (en) | 2019-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6622088B2 (en) | Polyurethane foam by reaction injection molding | |
| EP2336209A2 (en) | Fire-resistant polyurethane foam and fabrication method thereof | |
| CN103998500B (en) | Comprise the single-layer flexible foams of polyurethane gle | |
| TW201829523A (en) | Thermoplastic polyurethane resin for foaming and production method thereof, and molded article | |
| JP6535827B2 (en) | Polyurethane water dispersion, method of producing polyurethane water dispersion, water-based paint composition and coating film | |
| JP6499347B1 (en) | Polyurethane resin composition | |
| JP2012082273A (en) | Fire resistant polyurethane foam and manufacturing method thereof | |
| CN108329855A (en) | Sticker and adhesive sheet | |
| CN106866913A (en) | The method that one-step method prepares foaming type polyurethane resin | |
| CN103820019A (en) | Water-based polyurethane-containing stripping coating and preparation method thereof | |
| CN108424728A (en) | Sticker and adhesive sheet | |
| CN104017159B (en) | A kind of powder-type aqueous polyurethane and preparation method thereof | |
| JPWO2020075651A1 (en) | Manufacturing method of foamed polyurethane elastomer raw material, foamed polyurethane elastomer, midsole and foamed polyurethane elastomer | |
| CN106866910B (en) | The method of two-step method preparation foaming type polyurethane resin | |
| WO2014030452A1 (en) | Urethane resin composition, leather-like sheet, and laminate | |
| CN114015227B (en) | Quick-curing slow-rebound acrylic foam and preparation method and application thereof | |
| KR20170002955A (en) | Rigid polyurethane foam for insulator and method for manufacturing the same | |
| JP5271548B2 (en) | Hardly discolorable soft polyurethane foam | |
| JP2008094944A (en) | Process for producing flexible polyurethane foam | |
| WO2018148231A1 (en) | Reactive hot-melt adhesive composition containing a polyester-polyurethane | |
| JP6259561B2 (en) | Cleaning roller and method for producing polyurethane foam used for cleaning roller | |
| CN110461896B (en) | Urethane synthetic leather, method for producing urethane synthetic leather, cosmetic puff, and member with synthetic leather | |
| JP7032177B2 (en) | Flexible polyurethane foam | |
| KR101804939B1 (en) | Starch sugar-based waterborne polyurethane resin and manufacturing method thereof | |
| JP2001185216A (en) | Gelatinous electrolyte and manufacturing method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |