CN110003423A - Modified isocyanate performed polymer, polyurethane combined material and its preparation method and application - Google Patents
Modified isocyanate performed polymer, polyurethane combined material and its preparation method and application Download PDFInfo
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- CN110003423A CN110003423A CN201910211344.XA CN201910211344A CN110003423A CN 110003423 A CN110003423 A CN 110003423A CN 201910211344 A CN201910211344 A CN 201910211344A CN 110003423 A CN110003423 A CN 110003423A
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- acid
- polyol
- isocyanates
- modified isocyanate
- polyurethane
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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
- C08G18/08—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
-
- 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
- C08G18/4054—Mixtures of compounds of group C08G18/60 with other macromolecular compounds
-
- 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
- C08G18/48—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
- C08G18/40—High-molecular-weight compounds
- C08G18/60—Polyamides or polyester-amides
- C08G18/603—Polyamides
Abstract
The invention discloses a kind of modified isocyanate performed polymers, polyurethane combined material and its preparation method and application, the modified isocyanate performed polymer is isocyanates and the reaction product with the polymer (A) for being in reactive group to isocyanates, has and contains low-molecular-weight polyamide resin polyalcohol in the polymer (A) of reactive group to isocyanates.Polyurethane combined material includes polyol blends and modified isocyanate performed polymer；Polyurethane combined material can be used for preparing high-performance polyamide-polyurethane hybridization material.The additive amount range of filler particles of the present invention is wide, and hybrid material elasticity is good, and density and hardness adjustable extent is wide, using wide.The addition of low-molecular-weight polyamide resin polyalcohol improves the heat resistance of hybrid material, it is made to can be applied to hot environment.
Description
Technical field
The present invention relates to low molecular polyamides modified isocyanate performed polymer, polyurethane combined material and preparation method thereof and
Using.
Background technique
Polyurethane is a kind of high molecular material containing carbamate constitutional repeating unit, has intensity height, physical property tune
The advantages that adjusting range is wide, process operability is good, is widely used in the fields such as daily life, industrial and agricultural production and medicine.In poly- ammonia
Other materials are filled in ester material or prepare composite material in conjunction with other materials, can further promote the specificity of polyurethane
Production cost can or be reduced, the application field of compound polyurethane material is expanded.As ZL201210562641.7 discloses polyurethane original
Liquid component A, B component and waste and old rubber particle are uniformly mixed production polyurethane shoe-sole, improve sole using waste and old rubber particle
Tensile strength, wearability, tear-resistant intensity etc..WO 2008/087078 disclose the matrix comprising being made of polyurethane and comprising
The hybrid material of thermoplastic polyurethane foam particle in the base.By isocyanates, have have to isocyanates it is reactive
Compound, chain extender and/or the crosslinking agent of hydrogen atom, catalyst and other additives prepare isocyanate prepolymer, then will
Isocyanate prepolymer is mixed with the foaming example of thermoplastic polyurethane, and solidifies composite material by the effect of water.WO
2014/023794 discloses the matrix comprising being made of polyurethane foam and comprising thermoplastic polyurethane foam particle in the base
Composition foam, wherein matrix and each free polyol component of particle and polyisocyanate component composition, wherein at least 50 weights
Amount %'s be used to form that matrix is identical with the basic structural unit of the polyol component of particle, and at least 50 weight % are used for shape
It is identical with the base structure unit of the polyisocyanate component of particle at matrix, the wherein foaming in the complete aperture of matrix and matrix
Particle at least partly aperture.A kind of low-molecular-weight polyamide resin polyalcohol is disclosed, is the combination of polyamide and polyurethane
Condition is provided, rigid coating is made in polyurethane, can be applied to the fields such as metal, glass, woodenware.
Summary of the invention
The object of the present invention is to provide a kind of modified isocyanate performed polymer, polyurethane combined material and preparation method thereof and answer
With to overcome defect of the existing technology.
The modified isocyanate performed polymer are as follows: isocyanates and with to isocyanates be in reactive group polymer
(A) reaction product, it is described that there is the polymer (A) for being in reactive group to isocyanates to contain low-molecular-weight polyamide resin
Polyalcohol；
The number-average molecular weight of the low-molecular-weight polyamide resin polyalcohol be 700~2000, preferably binary acid,
The reaction product of diamine, hydramine；Preparation method can be found in described in CN 104231260A.
Preferably, described also to contain polyester polyol, polyethers with the polymer (A) for isocyanates being in reactive group
One or more of polyalcohol；
The degree of functionality with the polymer (A) for isocyanates being in reactive group is 2~3, and number-average molecular weight is
700~10000.
The NCO content of the modified isocyanate performed polymer is 0.1wt%~15.0wt%, it is preferred that the modification
The NCO content of Isocyanate prepolymers body is 0.1wt%~10.0wt%.
The polyester polyol is by the organic dicarboxylic acid containing 2~14 carbon atoms and containing the polyalcohol of 2~14 carbon atoms
Esterification obtains, and degree of functionality is 2~3, and number-average molecular weight is 1000~6000；
The organic dicarboxylic acid be adipic acid, succinic acid, glutaric acid, suberic acid, decanedioic acid, azelaic acid, phthalic acid,
One or more of terephthalic acid (TPA), M-phthalic acid, dodecanedioic acid, maleic acid, fumaric acid；
The polyalcohol be ethylene glycol, diethylene glycol, 1,2- or 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,
One or more of 6- hexylene glycol, glycerol, trimethylolpropane；
The polyester polyol can also be polycaprolactone polyol, one or more of polycarbonate polyol；
The polyether polyol is polyoxypropylene polyol, polyoxyethylated polyols, polyethylene glycol oxide-propylene oxide
One or more of polyol, polytetrahydrofuran diol, polytetrahydrofuran copolymer diol, polytrimethylene ether glycol；
The degree of functionality of the polyether polyol is 2~3, and number-average molecular weight is 1000~10000；
The isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, Carbodiimide-Modified hexichol
Dicyclohexylmethane diisocyanate, uretonimine-modified methyl diphenylene diisocyanate, isophorone diisocyanate, tetramethylene
One or more of diisocyanate, hexamethylene diisocyanate, methylene two (cyclohexyl diisocyanate).
The preparation method of the modified isocyanate performed polymer, includes the following steps:
By isocyanates and with the polymer (A) for isocyanates being in reactive group, 2.0 are reacted at 75~85 DEG C
~3.0h can be obtained the modified isocyanate performed polymer；It is preferably added in reaction raw materials and accounts for total mass of raw material
The phosphoric acid of 0.002wt%~0.020wt%；
The invention further relates to a kind of polyurethane combined material, the polyurethane combined material includes polyol blends and described
Modified isocyanate performed polymer；
The hydroxyl (- OH) of the polyol blends and the isocyanate group (- NCO) in modified isocyanate performed polymer
Molar ratio is 1:(1.0~1.1)；
The polyol blends include with polymer (B), the chain extender, foaming for being in reactive group to isocyanates
Agent, foam stabilizer and catalyst；
The parts by weight of each raw material in the polyol blends are as follows:
Preferably, the polyol blends also include antioxidant, antistatic agent, anti-wear agent, the antioxidant, resist it is quiet
The dosage of electric agent and anti-wear agent be the 0.01wt% with polymer (B) quality for isocyanates being in reactive group~
3.0wt%；
It is low-molecular-weight polyamide resin polyalcohol, polyester to isocyanates with the polymer (B) for being in reactive group
One or more of polyalcohol, polyether polyol；
The low-molecular-weight polyamide resin polyalcohol is the reaction product of binary acid, diamine, hydramine, and molecular weight is
700~2000；Preparation method is as described in CN 104231260A；
The polyester polyol is by the organic dicarboxylic acid containing 2~14 carbon atoms and containing the polyalcohol of 2~14 carbon atoms
Esterification, degree of functionality are 2~3, and number-average molecular weight is 1000~6000；
The organic dicarboxylic acid be adipic acid, succinic acid, glutaric acid, suberic acid, decanedioic acid, azelaic acid, phthalic acid,
One or more of terephthalic acid (TPA), M-phthalic acid, decane dicarboxylic acid, maleic acid, fumaric acid；
The polyalcohol be ethylene glycol, diethylene glycol, 1,2- or 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,
One or more of 6- hexylene glycol, glycerol, trimethylolpropane.
The polyester polyol can also be polycaprolactone polyol, one or more of polycarbonate glycol.
The polyether polyol is polyoxypropylene polyol, polyoxyethylated polyols, polyethylene glycol oxide-propylene oxide
One or more of polyol, polytetrahydrofuran diol, polytetrahydrofuran copolymer diol, polytrimethylene ether glycol；
The degree of functionality of the polyether polyol is 2~3, and number-average molecular weight is 1000~10000.
The chain extender is the dihydric alcohol of molecular weight 62g/mol~500g/mol；
The foaming agent is one or more of water, pentamethylene, pentane, supercritical carbon dioxide；
The foam stabilizer is organic foam stabilizer；
The catalyst is triethylene diamine and/or stannous octoate.
The preparation method of the polyol blends, includes the following steps:
To have and exists to isocyanates in polymer (B), chain extender, foaming agent, foam stabilizer, the catalyst of reactive group
2.5~3.5h is mixed at 40~45 DEG C, the polyol blends can be obtained in discharging；
The polyurethane combined material can be used for preparing high-performance polyamide-polyurethane hybridization material, and application method is as follows:
The temperature for maintaining polyol blends in polyurethane combined material is 20~40 DEG C, low molecular weight in polyurethane combined material
40~70 DEG C of temperature of the polyalcohol modified Isocyanate prepolymers body of polyamide are 1:(1.0 by the molar ratio of-OH and-NCO
~1.1) polyol blends, modified isocyanate performed polymer are uniformly mixed with filler particles, injects (50~80) DEG C mold
(3~8) min molding is reacted, demoulding cures (45~50) h, can be obtained the high-performance polyamide-polyurethane hybrid material
Material；
The filler particles are thermoplastic polyurethane foam particle, CPU elastomer particles, rubber grain, ethyl vinyl acetate second
One or more of alkene copolymer (EVA) particle, thermoplastic polyester expanded beads；
The additive amount of the filler particles is 1wt%~90wt% of hybrid material gross mass.
The diameter of the filler particles is 0.1cm to 10cm, and is spherical or ellipse.
The filler particles are tubular particle, and length is 1mm to 40mm, and diameter is 1mm to 40mm.
High-performance polyamide-polyurethane hybridization material the density is 0.10g/cm3To 1.20g/cm3；
High-performance polyamide-the polyurethane hybridization material for sole, saddle of bicycle, sports equipment, adventure playground,
Upholstery, automobile interior exterior decorations, athletic tracks.
Beneficial effects of the present invention: system rise time is long, the polyurethane of low-molecular-weight polyamide resin polyalcohol enhancing
High with the cementability of filler particles, the additive amount range of filler particles is wide, can effectively adhesion height filling without using adhesive
The particle of amount, hybrid material demoulding time obtained is short, and elasticity is good, and density and hardness adjustable extent is wide, using wide.Low molecular weight
The addition of polyamide polyalcohol improves the heat resistance of hybrid material, it is made to can be applied to hot environment.
Specific embodiment
Below by specific embodiment, the present invention is further elaborated, it should be understood that reality of the invention
Specific material proportion described in example is applied, process conditions and result are merely to illustrate the present invention, this can not be limited with this
The protection scope of invention, the equivalent change or modification that all Spirit Essences according to the present invention are done, should all cover in this hair
In bright protection scope.
The preparation of modified isocyanate performed polymer:
Embodiment 1
By the MDI of 10.0kg, the polyamide polyalcohol (number-average molecular weight 700) of 6.6kg, 0.40kg's gathers oneself two
Sour glycol ester glycol (number-average molecular weight 1000), the phosphoric acid of 0.34g react 3.0h at 75 DEG C, and it is poly- to obtain low molecular weight
The polyalcohol modified Isocyanate prepolymers body 1 of amide resin, NCO content 15.0wt%.
Embodiment 2
By the MDI of 10.0kg, the polyamide polyalcohol (number-average molecular weight 2000) of 5.2kg, 4.8kg's gathers oneself two
Sour glycol ester glycol (number-average molecular weight 2000), the Polyoxypropylene diol (number-average molecular weight 2000) of 6.0kg,
The phosphoric acid of 2.6g reacts 2.0h at 80 DEG C, obtains the polyalcohol modified Isocyanate prepolymers body 2 of low-molecular-weight polyamide resin,
NCO content is 10.3wt%.
Embodiment 3
By the MDI of 10.0kg, the polyamide polyalcohol (number-average molecular weight 1400) of 13.6kg, 9.2kg's gathers oneself
Naphthalate glycol (number-average molecular weight 1500), (number-average molecular weight is the Polyoxypropylene diol of 15.6kg
1500), the phosphoric acid of 9.68g reacts 2.5h at 85 DEG C, and it is pre- to obtain the polyalcohol modified isocyanates of low-molecular-weight polyamide resin
Aggressiveness 3, NCO content 2.4wt%.
Embodiment 4
By the MDI of 10.0kg, (number is equal for the polyamide polyalcohol of the Carbodiimide-Modified MDI, 23.9kg of 0.83kg
Molecular weight is 2000) the polyethylene glycol adipate glycol (number-average molecular weight 1500) of 18.8kg, the polyoxygenated third of 19.3kg
Alkene dihydric alcohol (number-average molecular weight 2000), the phosphoric acid of 9.68g react 2.5h at 85 DEG C, obtain low molecular polyamides tree
The polyalcohol modified Isocyanate prepolymers body 4 of rouge, NCO content 1.0wt%.
The preparation of polyurethane combined material and hybrid material:
By table 1 by polyamide polyalcohol, polyester polyol, polyether polyol, chain extender, foaming agent, foam stabilizer, urge
The mixing such as agent, antioxidant, wherein embodiment 5~7 mixes 3.5h at 40 DEG C, and embodiment 8~9 is mixed at 45 DEG C
2.5h, discharging are sealed, and obtain polyol-mixture component.
The temperature for maintaining polyol blends in the polyurethane combined material in embodiment 5~6 is 20 DEG C, polyurethane combined material
The temperature of the middle polyalcohol modified Isocyanate prepolymers body of low-molecular-weight polyamide resin is 40 DEG C, remains poly- in embodiment 7~9
The temperature of polyol blends is 40 DEG C in urethane combination material, and low-molecular-weight polyamide resin polyalcohol changes in polyurethane combined material
Property Isocyanate prepolymers body temperature be 70 DEG C, it is by table 1 that polyol blends, low-molecular-weight polyamide resin is polyalcohol modified
Isocyanate prepolymers body is uniformly mixed with filler particles, and embodiment 5 injects 50 DEG C of mold reaction 3min moldings, is demoulded, curing
46h, embodiment 6 inject 60 DEG C of mold reaction 4min moldings, and demoulding cures 45h, and embodiment 7 and embodiment 9 inject 70 DEG C of molds
6min molding is reacted, demoulding cures 48h, and embodiment 8 injects 80 DEG C of mold reaction 8min moldings, and demoulding cures 50h, all obtains
High-performance polyamide-polyurethane hybridization material.
Table 1
It is by table 2 that polyester polyol, polyether polyol, chain extender, foaming agent, foam stabilizer, catalyst, antioxidant etc. is mixed
It closes, wherein comparative example 1~2 mixes 3.5h at 40 DEG C, and embodiment 3~5 mixes 2.5h at 60 DEG C, and discharging is sealed, and obtains
To polyol-mixture component.
By isocyanates, polyester polyol, polyether polyol, reaction kettle is added in phosphoric acid, is reacted at (75~85) DEG C
(2.0~3.0) h, wherein comparative example 1 and comparative example 5 mix 3.0h at 75 DEG C, and comparative example 2 is in 80 DEG C of reaction 2.0h comparative examples 3
~4 react 2.5h at 85 DEG C, and discharging is sealed, and obtain Isocyanate prepolymers body.
The temperature for maintaining polyol blends in the polyurethane combined material in comparative example 1~3 is 20 DEG C, polyurethane combined material
The temperature of middle performed polymer is 40 DEG C, and maintaining the temperature of polyol blends in the polyurethane combined material in comparative example 4~5 is 40
DEG C, the temperature of Isocyanate prepolymers body is 60 DEG C in polyurethane combined material, by table 1 by polyol blends, Isocyanate prepolymers
Body is uniformly mixed with filler particles, and comparative example 1 injects 50 DEG C of mold reaction 3min moldings, and demoulding cures 46h, and comparative example 2 is injected
60 DEG C of mold reaction 4min moldings, demoulding cure 45h, and comparative example 3 and embodiment 5 are injected 70 DEG C of mold reaction 6min moldings, taken off
Mould cures 48h, and comparative example 4 injects 80 DEG C of mold reaction 8min moldings, and demoulding cures 50h, all obtains polyurethane material.
Table 2
Poly- ammonia made from the polyamide of high-performance made from Application Example 5~9-polyurethane hybridization material and comparative example 1~5
Every physical property measurement result of ester material is listed in table 3.Wherein: compact density is detected using GB/T 1033.1-2008 method, at
Type hardness tester (Shao A) is detected using GB/T 531.1-2008 method, and TGA thermal weight loss rate is detected using thermal gravimetric analyzer, and tension is strong
It spends (MPa) and elongation (%) to detect using GB/T 528-2009 method, tearing strength (kN/m) uses GB/T 529-2008
Method detection, rise time are measured using HG/T 4574-2014.
Table 3
Wherein TGA thermal weight loss rate uses polyurethane combined material producing foamed body, is free of filler particles, is tested.Implement
Example 8 and 4 hardness test of comparative example are without as a result, since the elastomeric material is very soft, suitable for answering hardness requirement is low-down
Use field.By table 3, it is known that, system rise time of the present invention is long, low-molecular-weight polyamide resin polyalcohol enhancing polyurethane with
The cementabilities of filler particles is high, and the additive amount range of filler particles is wide, without using adhesive can effective adhesion filler particles,
Manufactured hybrid material demoulding time is short, and elasticity is good, and density and hardness adjustable extent is wide, using wide.Add low molecular weight polyamides
Polyimide resin polyalcohol improves the heat resistance of hybrid material, it is made to can be applied to hot environment.
Although above-described embodiment is described in detail technical solution of the present invention, technical side of the invention
Case is not limited to above embodiments, when not departing from thought and objective of the invention, to scope of the present invention patent
Equivalent change or modification made by content all should be technology scope of the invention.
Claims (18)
1. modified isocyanate performed polymer, which is characterized in that for isocyanates and with to isocyanates in reactive group
The reaction product of polymer (A), it is described to contain low molecular weight polyamides with the polymer (A) for isocyanates being in reactive group
Polyimide resin polyalcohol.
2. modified isocyanate performed polymer according to claim 1, which is characterized in that the low molecular polyamides tree
The number-average molecular weight of rouge polyalcohol is 700~2000.
3. modified isocyanate performed polymer according to claim 1, which is characterized in that the low molecular polyamides tree
Rouge polyalcohol is the reaction product of binary acid, diamine, hydramine.
4. modified isocyanate performed polymer according to claim 1, which is characterized in that described to have to isocyanates in anti-
The degree of functionality of the polymer (A) of answering property group is 2~3, and number-average molecular weight is 700~10000.
5. modified isocyanate performed polymer according to claim 1, which is characterized in that described to have to isocyanates in anti-
The polymer (A) of answering property group also contains one or more of polyester polyol, polyether polyol.
6. modified isocyanate performed polymer according to claim 1, which is characterized in that the modified isocyanate performed polymer
NCO content be 0.1wt%~15.0wt%.
7. modified isocyanate performed polymer according to claim 5, which is characterized in that the polyester polyol by containing 2~
The organic dicarboxylic acid of 14 carbon atoms reacts acquisition with the polyhydric alcohol containing 2~14 carbon atoms, and degree of functionality is 2~3, and number is equal
Molecular weight is 1000~6000, and the polyether polyol is polyoxypropylene polyol, polyoxyethylated polyols, polyoxyethylene
Alkene-propylene oxide polyol, polytetrahydrofuran diol, polytetrahydrofuran copolymer diol, in polytrimethylene ether glycol
More than one, the degree of functionality of the polyether polyol is 2~3, and number-average molecular weight is 1000~10000.
8. modified isocyanate performed polymer according to claim 7, which is characterized in that the organic dicarboxylic acid for oneself two
Acid, succinic acid, glutaric acid, suberic acid, decanedioic acid, azelaic acid, phthalic acid, terephthalic acid (TPA), M-phthalic acid, laurel two
One or more of acid, maleic acid, fumaric acid；
The polyalcohol be ethylene glycol, diethylene glycol, 1,2- or 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,6- oneself
One or more of glycol, glycerol, trimethylolpropane, the polyester polyol can also be polycaprolactone polyol, gather
One or more of carbonate polyol.
9. modified isocyanate performed polymer according to claim 1, which is characterized in that the isocyanates is that toluene two is different
Cyanate, methyl diphenylene diisocyanate, carbodiimide modified diphenylmethane diisocyanate, uretonimine-modified two
Methylenebis phenyl isocyanate, isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate,
One or more of methylene two (cyclohexyl diisocyanate).
10. the preparation method of described in any item modified isocyanate performed polymers according to claim 1~9, which is characterized in that packet
It includes following steps: by isocyanates and with the polymer (A) for isocyanates being in reactive group, being reacted at 75~85 DEG C
2.0~3.0h can be obtained the modified isocyanate performed polymer.
11. according to the method described in claim 10, accounting for total mass of raw material it is characterized in that, being added in reaction raw materials
The phosphoric acid of 0.002wt%~0.020wt%.
12. polyurethane combined material, which is characterized in that change comprising polyol blends and claim 1~11 are described in any item
Property Isocyanate prepolymers body；The hydroxyl (- OH) and the isocyanates in modified isocyanate performed polymer of the polyol blends
The molar ratio of base (- NCO) is 1:(1.0~1.1).
13. polyurethane combined material according to claim 12, which is characterized in that the polyol blends include have pair
Isocyanates is in polymer (B), chain extender, foaming agent, foam stabilizer and the catalyst of reactive group；The polyol blends
In each raw material parts by weight are as follows:
14. polyurethane combined material according to claim 13, which is characterized in that the polyol blends also include anti-
Oxygen agent, antistatic agent, anti-wear agent, the dosage of the antioxidant, antistatic agent and anti-wear agent be with to isocyanates in reaction
0.01wt%~the 3.0wt% of polymer (B) quality of property group.
15. polyurethane combined material according to claim 13, which is characterized in that described has to isocyanates in reaction
Property group polymer (B) be one of low-molecular-weight polyamide resin polyalcohol, polyester polyol, polyether polyol with
On；
The low-molecular-weight polyamide resin polyalcohol be binary acid, diamine, hydramine reaction product, molecular weight be 700~
2000；
The polyester polyol is by the organic dicarboxylic acid containing 2~14 carbon atoms and containing the polyhydric alcohol of 2~14 carbon atoms
Reaction, degree of functionality are 2~3, and number-average molecular weight is 1000~6000；
The organic dicarboxylic acid be adipic acid, succinic acid, glutaric acid, suberic acid, decanedioic acid, azelaic acid, phthalic acid, to benzene
One or more of dioctyl phthalate, M-phthalic acid, decane dicarboxylic acid, maleic acid, fumaric acid；
The polyalcohol be ethylene glycol, diethylene glycol, 1,2- or 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,6- oneself
One or more of glycol, glycerol, trimethylolpropane；
The polyester polyol can also be polycaprolactone polyol, one or more of polycarbonate glycol.
The polyether polyol is polyoxypropylene polyol, polyoxyethylated polyols, polyethylene glycol oxide-propylene oxide copolymerization
One or more of polyalcohol, polytetrahydrofuran diol, polytetrahydrofuran copolymer diol, polytrimethylene ether glycol；
The degree of functionality of the polyether polyol is 2~3, and number-average molecular weight is 1000~10000；
The chain extender is the dihydric alcohol of molecular weight 62g/mol~500g/mol；
The foaming agent is one or more of water, pentamethylene, pentane, supercritical carbon dioxide；
The foam stabilizer is organic foam stabilizer；
The catalyst is triethylene diamine and/or stannous octoate.
16. the application of 2~15 described in any item polyurethane combined materials according to claim 1, which is characterized in that be used to prepare height
Performance polyamide-polyurethane hybridization material.
17. application according to claim 16, which is characterized in that application method is as follows:
The temperature for maintaining polyol blends in polyurethane combined material is 20~40 DEG C, low molecular weight polyamides in polyurethane combined material
40~70 DEG C of temperature of the polyalcohol modified Isocyanate prepolymers body of polyimide resin, by the molar ratio of-OH and-NCO be 1:(1.0~
1.1) polyol blends, modified isocyanate performed polymer are uniformly mixed with filler particles, injection (50~80) DEG C mold is anti-
(3~8) min is answered to form, demoulding cures (45~50) h, can be obtained the high-performance polyamide-polyurethane hybridization material.
18. application according to claim 17, which is characterized in that the filler particles are thermoplastic polyurethane foam
Grain, CPU elastomer particles, rubber grain, ethylene-vinyl acetate copolymer (EVA) particle, in thermoplastic polyester expanded beads
More than one；
The additive amount of the filler particles is 1wt%~90wt% of hybrid material gross mass.
The diameter of the filler particles is 0.1cm to 10cm, and is spherical or ellipse.
The filler particles are tubular particle, and length is 1mm to 40mm, and diameter is 1mm to 40mm.
High-performance polyamide-polyurethane hybridization material the density is 0.10g/cm3To 1.20g/cm3。
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| CN117050264A (en) * | 2023-09-15 | 2023-11-14 | 东莞市森宏新材料科技有限公司 | Bio-based foaming insole and preparation process thereof |
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