CN106750132A - A kind of polyurethane foam vibration-absorptive material and preparation method thereof - Google Patents

A kind of polyurethane foam vibration-absorptive material and preparation method thereof Download PDF

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Publication number
CN106750132A
CN106750132A CN201611258437.0A CN201611258437A CN106750132A CN 106750132 A CN106750132 A CN 106750132A CN 201611258437 A CN201611258437 A CN 201611258437A CN 106750132 A CN106750132 A CN 106750132A
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China
Prior art keywords
polyurethane foam
absorptive material
preparation
polyurethane
vibration
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CN201611258437.0A
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Inventor
刘键
林德苗
闫路瑶
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Shenzhen city innovation Material Technology Co., Ltd.
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Zhongwu Function Material Institute Co Ltd
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Priority to CN201611258437.0A priority Critical patent/CN106750132A/en
Publication of CN106750132A publication Critical patent/CN106750132A/en
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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
    • 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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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    • C08J2203/00—Foams characterized by the expanding agent
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  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The preparation method of the polyurethane foam vibration-absorptive material that the present invention is provided, by shear thickening gel, compatilizer, polyurethane A material heating is mixed to form mixture, the mixture is mixed with modified MDI, it is foamed again, curing obtains polyurethane foam vibration-absorptive material, the preparation method of the polyurethane foam vibration-absorptive material that the present invention is provided, using polyurethane foam as matrix material, compound technical scheme is carried out with shear thickening gel, due to shear thickening gel, viscosity is very big in itself, it is difficult to directly disperse in polyurethane A material, during shear thickening gel is introduced, add compatilizer, simplify production technology, reduce side reaction probability of happening, product processes are easily controlled.

Description

A kind of polyurethane foam vibration-absorptive material and preparation method thereof
Technical field
The present invention relates to vibration-absorptive material field, more particularly to a kind of polyurethane foam vibration-absorptive material and preparation method thereof.
Background technology
Polyurethane foam has the function of buffering, is usually used in sofa furniture, pillow, cushion, toy, clothes and sound insulation liner. Traditional polyurethane foam products shock-absorbing function, it is main to utilize what polyurethane foam porous compressibility was realized.When this material The shortcoming that material is applied to be primarily present in physical protection or precision instrument protection is limited damping performance, by severe impact When, common protective materials fully can not effectively dissipate impact energy, still have very strong impact force action On human body or equipment, personal injury or device damage can be caused.These problems are produced, and have higher wanting to material property Ask.
Currently used most of impact shock mitigation system is polyurethane, EVA, the rubbery system of independent foaming.System Simply, damping, buffering performance is general, and when being applied to high-end buffering field, protection effect is limited.Existing more ripe technology, be The D3O products of Britain, matrix uses polyurethane, and temperature in use scope is -10 DEG C~+80 DEG C, for physical protection, it is impossible to It is used in temperature environment higher, such as engine, Long-term Vibration heat position.Current patent is related to shear thickening gel , also it is related to what gel and elastic polyurethane foam were combined, scattering problem of the gel in polymeric matrix is mainly solved, Have plenty of by energy-absorbing gel dispersion in organic solvent (such as isopropanol) or hydroxy silicon oil, both approaches have the drawback that Complex process is, it is necessary to removal solvent is while limit energy-absorbing filling adding amount, addition compatilizer promotes energy-absorbing to fill out during the course of the reaction Material more preferably disperses in polyurethane matrix, and the technology of preparing of polyurethane foam composite material is little, while polyurethane foam work Skill is ripe.
The content of the invention
Based on this, it is necessary to provide a kind of process is simple, the strong polyurethane foam vibration-absorptive material of damping energy absorption ability and its Preparation method.
By shear thickening gel, compatilizer, polyurethane A expect in temperature range be 40~100 DEG C under the conditions of be mixed to form it is mixed Compound；
The mixture is mixed with modified MDI, then foamed, curing obtains polyurethane foam vibration-absorptive material；
The polyurethane A material include the PPG that mass fraction is 5-35 parts, the polymerization that mass fraction is 5-35 parts Thing polyalcohol and mass fraction are 55-80 part of special polyether, the hydroxyl value of the polyalcohol of the special polyether is 300~ 380mgKOH/g, degree of functionality is 2.8~3.2, and the special polyether is with propane diols, glycerine, diethylene glycol (DEG) or trimethylolpropane In two or more as mixing initiator, by the ring-opening polymerisation of 1,2- expoxy propane or with oxirane copolymerization and obtain, wherein Mass content≤20% of oxirane.
In certain embodiments, the mass ratio of the compatilizer and the shear thickening gel is between 0.1%~10%, The shear thickening gel accounts for the 5%~45% of the polyurethane A material quality, and the polyurethane A material and MDI mass ratioes are 10: 2.5~10:8.
In certain embodiments, the compatilizer is dimethyl silicone polymer-polyethylene glycol, poly glycidyl ester, hydroxyl Silicone oil γ-methacryloxypropyl-trimethoxy silane, N- (β-aminoethyl)-γ-aminopropyl-Methyl-trimethoxy silicon At least one in alkane, γ-chloropropyl-trimethoxy silicon.
In certain embodiments, foaming agent, foam stabiliser, catalyst and chain extender are also included in the polyurethane A material.
In certain embodiments, the foaming agent is at least one of water, two perhaloalkenes classes, hydro carbons.
In certain embodiments, the foam stabiliser is organic silicon foam stabiliser.
In certain embodiments, the catalyst be triethylenediamine, dibutyl tin laurate, stannous octoate, N, At least one of N- dimethyl cyclohexyl amines, N-ethylmorpholine, triethanolamine.
In certain embodiments, the chain extender is dimethyl silicone polymer-polyethylene glycol, poly glycidyl ester, diethyl Alkenyl tetramethyl disiloxane, vinyl triethoxyl siloxanes, vinyl trichlorosilane, vinyl three (beta-methoxy ethyoxyl) Silane, γ-glycidylpropyl-trimethoxy silane, γ-methacryloxypropyl-trimethoxy silane, N- (β-ammonia Ethyl)-γ-aminopropyl-Methyl-trimethoxy silane, γ-chloropropyl-trimethoxy silicon, γ-mercapto propyl-trimethoxysilane At least one of with N- (β-aminoethyl)-γ-aminopropyl-trimethoxy silane.
In certain embodiments, mix with modified MDI by the mixture, then foamed, curing obtains polyurethane In the step of foam vibration-absorptive material, specially：Mix with modified MDI by the mixture, be placed in mould and foam, and protect 4~15min of pressure time, normal temperature cures 12~72h and obtains polyurethane foam vibration-absorptive material after taking-up, and the temperature of the mould is 45 ~80 DEG C.
In addition present invention also provides the polyurethane foam that the preparation method of above-mentioned polyurethane foam vibration-absorptive material is prepared Foam vibration-absorptive material.
The preparation method of the polyurethane foam vibration-absorptive material that the present invention is provided, by shear thickening gel, compatilizer, polyurethane A material heating is mixed to form mixture, and the mixture is mixed with modified MDI, then foamed, curing obtains polyurethane foam Vibration-absorptive material, the preparation method of the polyurethane foam vibration-absorptive material that the present invention is provided, using polyurethane foam as matrix material, with Shear thickening gel carries out compound technical scheme, and due to shear thickening gel, viscosity is very big in itself, it is difficult to directly in polyurethane A Disperse in material, during shear thickening gel is introduced, add compatilizer, simplify production technology, reduce side reaction hair Raw probability, product processes are easily controlled.
Brief description of the drawings
The step of Fig. 1 is the preparation method of the polyurethane foam vibration-absorptive material of implementation method flow chart.
Specific embodiment
To enable the above objects, features and advantages of the present invention more obvious understandable, below in conjunction with the accompanying drawings to the present invention Specific embodiment be described in detail.Elaborate many details in order to fully understand this hair in the following description It is bright.But the present invention can be implemented with being much different from other manner described here, and those skilled in the art can be not Similar improvement is done in the case of running counter to intension of the present invention, therefore the present invention is not limited by following public specific implementation.
As shown in figure 1, the preparation method of the polyurethane foam vibration-absorptive material of an implementation method, comprises the following steps：
Step S110：Shear thickening gel, compatilizer, polyurethane A are expected to be mixed under the conditions of temperature range is for 40~100 DEG C Conjunction forms mixture；
Wherein, the polyurethane A material include that PPG, mass fraction that mass fraction is 5-35 parts are 5-35 parts Polymer polyatomic alcohol and the special polyether that mass fraction is 55-80 parts.
Preferably, the mass ratio of the compatilizer and the shear thickening gel is between 0.1%~10%, the shearing Thickened gel accounts for the 5%~45% of the polyurethane A material quality, and the polyurethane A material and MDI mass ratioes are 10:2.5~10: 8。
Specifically, the hydroxyl value of the polyalcohol of the special polyether is 300~380mgKOH/g, and degree of functionality is 2.8~3.2, The special polyether using two or more in propane diols, glycerine, diethylene glycol (DEG) or trimethylolpropane as mixing initiator, Obtained, mass content≤20% of its ethylene oxide by the ring-opening polymerisation of 1,2- expoxy propane or with oxirane copolymerization.
Preferably, the compatilizer is in dimethyl silicone polymer-polyethylene glycol, poly glycidyl ester and hydroxy silicon oil It is at least one.
Further, foaming agent, foam stabiliser, catalyst and chain extender are also included in the polyurethane A material.
The foaming agent is at least one of water, two perhaloalkenes classes, hydro carbons.
The foam stabiliser is organic silicon foam stabiliser.
The catalyst be triethylenediamine, dibutyl tin laurate, stannous octoate, N, N- dimethyl cyclohexyl amines, At least one of N-ethylmorpholine, triethanolamine.
The chain extender is dimethyl silicone polymer-polyethylene glycol, poly glycidyl ester, the silica of divinyl tetramethyl two Alkane, vinyl triethoxyl siloxanes, vinyl trichlorosilane, vinyl three (beta-methoxy ethyoxyl) silane, γ-glycidol Propyl-trimethoxysilane, γ-methacryloxypropyl-trimethoxy silane, N- (β-aminoethyl)-γ-aminopropyl- Methyl-trimethoxy silane, γ-chloropropyl-trimethoxy silicon, γ-mercapto propyl-trimethoxysilane and N- (β-aminoethyl)- At least one of γ-aminopropyl-trimethoxy silane.
Step S120：By the mixture and modified (methyl diphenylene diisocyanate MDI；Diphenyl- Methane-diisocyanate) mix, then foamed, curing obtains polyurethane foam vibration-absorptive material；
In the present embodiment, the mixture is mixed with modified MDI, is placed in mould and foams, and the dwell time 4~ 15min, normal temperature cures 12~72h and obtains polyurethane foam vibration-absorptive material after taking-up, and the temperature of the mould is 45~80 DEG C.
The preparation method of the polyurethane foam vibration-absorptive material that the present invention is provided, using polyurethane foam as matrix material, with Dilatant type gel carries out compound technical scheme, and due to shear thickening gel, viscosity is very big in itself, it is difficult to directly in polyurethane A material Middle dispersion, during shear thickening gel is introduced, adds compatilizer, simplifies production technology, reduces side reaction generation Probability, product processes are easily controlled.
Below with reference to specific embodiment, further to the preparation of the polyurethane foam vibration-absorptive material of embodiment of the present invention Method is illustrated.
Embodiment 1
Shear thickening gel, dimethyl silicone polymer-polyethylene glycol, polyol blends, water, organic silicon foam is steady Determine agent, triethylenediamine, dimethyl silicone polymer-polyethylene glycol in temperature range be 40 DEG C under the conditions of be mixed to form mixing Thing；B material (modified MDI) is poured into mixture, is quickly stirred, poured into mould and foam, 45 DEG C of mold temperature, during pressurize Between 4min, take out sheet material normal temperature curing 45h and obtain polyurethane foam vibration-absorptive material.
Embodiment 2
Shear thickening gel, poly glycidyl ester, polyol blends, two perhaloalkenes classes, organic silicon foam is steady Determine agent, dibutyl tin laurate and be mixed to form mixture under the conditions of being 100 DEG C in temperature range；B material (modified MDI) is poured into In mixture, quickly stir, pour into mould and foam, 80 DEG C of mold temperature, dwell time 15min takes out sheet material normal temperature Curing 72h obtains polyurethane foam vibration-absorptive material.
Embodiment 3
Shear thickening gel, hydroxy silicon oil, polyol blends, hydro carbons, organic silicon foam stabiliser, octanoic acid is sub- Tin, divinyl tetramethyl disiloxane are mixed to form mixture under the conditions of being 60 DEG C in temperature range；B is expected into (modified MDI) Pour into mixture, quickly stir, pour into mould and foam, 60 DEG C of mold temperature, dwell time 10min takes out sheet material Normal temperature curing 36h obtains polyurethane foam vibration-absorptive material.
Embodiment 4
Shear thickening gel, hydroxy silicon oil, polyol blends, hydro carbons, organic silicon foam stabiliser, octanoic acid is sub- Tin, vinyl triethoxyl siloxanes are mixed to form mixture under the conditions of being 70 DEG C in temperature range；B material (modified MDI) is fallen Enter in mixture, quickly stir, pour into mould and foam, 70 DEG C of mold temperature, dwell time 12min takes out sheet material normal Temperature curing 48h obtains polyurethane foam vibration-absorptive material.
Embodiment 5
By shear thickening gel, hydroxy silicon oil, polyol blends, two perhaloalkenes classes, organic silicon foam stabiliser, Triethanolamine, vinyl trichlorosilane are mixed to form mixture under the conditions of being 80 DEG C in temperature range；B material (modified MDI) is fallen Enter in mixture, quickly stir, pour into mould and foam, 80 DEG C of mold temperature, dwell time 10min takes out sheet material normal Temperature curing 36h obtains polyurethane foam vibration-absorptive material.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention Shield scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (10)

1. a kind of preparation method of polyurethane foam vibration-absorptive material, it is characterised in that comprise the following steps：
Shear thickening gel, compatilizer, polyurethane A are expected to be mixed to form mixture under the conditions of temperature range is for 40~100 DEG C；
The mixture is mixed with modified MDI, then foamed, curing obtains polyurethane foam vibration-absorptive material；
The polyurethane A material include that the PPG that mass fraction is 5-35 parts, the polymer that mass fraction is 5-35 parts are more First alcohol and the special polyether that mass fraction is 55-80 parts, the hydroxyl value of the polyalcohol of the special polyether is 300~380mgKOH/ G, degree of functionality is 2.8~3.2, the special polyether with two kinds in propane diols, glycerine, diethylene glycol (DEG) or trimethylolpropane or It is various as mixing initiators, by the ring-opening polymerisation of 1,2- expoxy propane or with oxirane copolymerization and obtain, its ethylene oxide Mass content≤20%.
2. the preparation method of polyurethane foam vibration-absorptive material as claimed in claim 1, it is characterised in that
Between 0.1%~10%, the shear thickening gel is accounted for the mass ratio of the compatilizer and the shear thickening gel The 5%~45% of the polyurethane A material quality, the polyurethane A material and MDI mass ratioes are 10:2.5~10:8.
3. the preparation method of polyurethane foam vibration-absorptive material as claimed in claim 2, it is characterised in that the compatilizer is poly- Dimethyl siloxane-polyethylene glycol, poly glycidyl ester and hydroxy silicon oil γ-methacryloxypropyl-trimethoxy silicon At least one in alkane, N- (β-aminoethyl)-γ-aminopropyl-Methyl-trimethoxy silane, γ-chloropropyl-trimethoxy silicon.
4. the preparation method of polyurethane foam vibration-absorptive material as claimed in claim 4, it is characterised in that the polyurethane A material In also include foaming agent, foam stabiliser, catalyst and chain extender.
5. the preparation method of polyurethane foam vibration-absorptive material as claimed in claim 4, it is characterised in that the foaming agent is At least one of water, two perhaloalkenes classes, hydro carbons.
6. the preparation method of polyurethane foam vibration-absorptive material as claimed in claim 4, it is characterised in that the foam stabiliser It is organic silicon foam stabiliser.
7. the preparation method of polyurethane foam vibration-absorptive material as claimed in claim 4, it is characterised in that the catalyst is three Ethylene diamine, dibutyl tin laurate, stannous octoate, N, in N- dimethyl cyclohexyl amines, N-ethylmorpholine, triethanolamine extremely Few one kind.
8. the preparation method of polyurethane foam vibration-absorptive material as claimed in claim 4, it is characterised in that the chain extender is poly- Dimethyl siloxane-polyethylene glycol, poly glycidyl ester, divinyl tetramethyl disiloxane, vinyl triethoxyl silica Alkane, vinyl trichlorosilane, vinyl three (beta-methoxy ethyoxyl) silane, γ-glycidylpropyl-trimethoxy silane, γ- Methacryloxypropyl-trimethoxy silane, N- (β-aminoethyl)-γ-aminopropyl-Methyl-trimethoxy silane, γ- Chloropropyl-trimethoxy silicon, γ-mercapto propyl-trimethoxysilane and N- (β-aminoethyl)-γ-aminopropyl-trimethoxy silane At least one of.
9. the preparation method of polyurethane foam vibration-absorptive material as claimed in claim 1, it is characterised in that by the mixture Mix with modified MDI, then during foamed, curing is the step of obtain polyurethane foam vibration-absorptive material, specially：Described will mix Compound mixes with modified MDI, is placed in mould and foams, and 4~15min of dwell time, and normal temperature cures 12~72h and obtains after taking-up To polyurethane foam vibration-absorptive material, the temperature of the mould is 45~80 DEG C.
10. a kind of preparation method using polyurethane foam vibration-absorptive material as claimed in any one of claims 1-9 wherein is prepared into The polyurethane foam vibration-absorptive material for arriving.
CN201611258437.0A 2016-12-30 2016-12-30 A kind of polyurethane foam vibration-absorptive material and preparation method thereof Pending CN106750132A (en)

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CN107415343A (en) * 2017-09-04 2017-12-01 天津工业大学 A kind of layer flexible buffering sandwich material and preparation method thereof
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CN107629465A (en) * 2017-10-18 2018-01-26 中国工程物理研究院化工材料研究所 A kind of silicone rubber impact hits energy-absorbing material and preparation method thereof
CN107629465B (en) * 2017-10-18 2020-05-22 中国工程物理研究院化工材料研究所 Silicone rubber impact-resistant energy-absorbing material and preparation method thereof
CN109438666A (en) * 2018-10-31 2019-03-08 湖南御邦华安新材料科技有限公司 Low temperature resistant, anti-ballistic materials and its preparation method and application
CN111995727A (en) * 2020-08-26 2020-11-27 王琴兰 Railway ballast bed vibration damping and shock pad composite material
CN114106554A (en) * 2021-11-25 2022-03-01 重庆长安汽车股份有限公司 Polyurethane/shear thickening gel composite material and application thereof in automobile seat
CN114316189A (en) * 2022-01-11 2022-04-12 中国科学院长春应用化学研究所 Impact-resistant protective thermoplastic polyurethane material and preparation method thereof
CN114316189B (en) * 2022-01-11 2022-11-01 中国科学院长春应用化学研究所 Impact-resistant protective thermoplastic polyurethane material and preparation method thereof

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