CN109438659A - A kind of non yellowing polyurethane material and preparation method thereof for crash dummy - Google Patents

A kind of non yellowing polyurethane material and preparation method thereof for crash dummy Download PDF

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Publication number
CN109438659A
CN109438659A CN201811068088.5A CN201811068088A CN109438659A CN 109438659 A CN109438659 A CN 109438659A CN 201811068088 A CN201811068088 A CN 201811068088A CN 109438659 A CN109438659 A CN 109438659A
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Prior art keywords
non yellowing
polyurethane material
crash dummy
aliphatic
agent
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CN201811068088.5A
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CN109438659B (en
Inventor
齐文斌
赵朝阳
张毅
董雨磊
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Shanghai He Cheng Polymer Science And Technology Ltd
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Shanghai He Cheng Polymer Science And Technology Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature

Abstract

The non yellowing polyurethane material and preparation method thereof that the present invention relates to a kind of for crash dummy, including aliphatic polyurethane performed polymer and chain extender.Product hardness of the invention reaches Shao A 55~75, appearance be it is colorless and transparent, there is good resilience, while there is good tension, tearing strength, the performances such as good weatherability, UV resistant, resistance to oxidation；Preparation process is simple, does not need special equipment, has a good application prospect.

Description

A kind of non yellowing polyurethane material and preparation method thereof for crash dummy
Technical field
The invention belongs to polyurethane field, in particular to a kind of non yellowing polyurethane material and its system for crash dummy Preparation Method.
Background technique
Along with the progress of society, people's lives level is higher and higher, and the rapid development of all kinds of vehicles, While bringing great convenience, also force people higher and higher to its security requirement.In the safety of the vehicles In test, the use of crash dummy is played a crucial role.Crash dummy using high molecular material simulation human skin and Muscle, high-strength material simulate skeleton, and the sensor by being mounted on each position embodies human body stress's situation and makes damage Determine.
On Vehicles Collected from Market crash dummy using more and more extensive, but be all to use plastics, rubber material, with human body Skin and texture, the intensity of muscle greatly differ from each other.What external import came, it is immediate with human body, also only use castor What sesame oil and calcium carbonate were made by mixing, the disadvantage is that:
1. material is easy to oxidize, human body surface easily changes colour, is dirty；
2. placement can return oil, surfaces of tacky long afterwards；
3. third is that material bad mechanical strength, elasticity, feel inequality；
It, need to be using large-scale vulcanizing equipment 4. dummy makes difficulty.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of non yellowing polyurethane material for crash dummy and its Preparation method, the Material texture will not change colour, and have good weatherability, non yellowing；Preparation process is simple, does not need special type and sets It is standby, it has a good application prospect.
The present invention provides a kind of non yellowing polyurethane materials for crash dummy, including aliphatic polyurethane performed polymer And chain extender；Wherein, by mass percentage, the raw material of aliphatic polyurethane performed polymer is polyether polyol 50~95% and fat 5~50wt% of (cyclo) aliphatic diisocyanates；The raw material of chain extender is small molecule amine 2~10%, polyether polyol 10~90%, other help Agent 0.1~5%.
The molecular weight of the polyether polyol is 300~4000, and degree of functionality is 2~4, is selected from GE-210, GE-220A, GE- 204、 RA-640、NT-403A、DV-125、MN-500、MN-700、MN-1000、MN-1500、MN-3050D、GEP-330N、 One or more of GE-303.
The aliphatic diisocyanate is hexamethylene diisocyanate HDI, HDI trimer, HDI biuret, different Buddhist You are ketone diisocyanate IPDI, dimethylene dicyclohexane diisocyanate H12One or more of MDI.
Isocyanate index NCO%=1~5% of the aliphatic polyurethane performed polymer.
The small molecule amine is 3,3 '-two chloro- 4,4 '-diphenylmethanediamiand MOCA, 3,5- dimethythiotoluene diamines DMTDA, 3,5- diethyl toluene diamine DETDA, 4,4 '-di-2-ethylhexylphosphine oxides (the chloro- 2,6- diethylaniline of 3-) MCDEA, 4,4 '- One or more of di-2-ethylhexylphosphine oxide (2,6- diethyl) aniline MDEA.
Other described auxiliary agents include 0.1~5wt% of levelling agent, 0.1~5wt% of defoaming agent, 0.5~5wt% of deicer, resist One or more of 0.2~0.5wt% of oxygen agent, 0.2~0.5wt% of UV light stabilizing agent, 0.1~5wt% of catalyst.
The levelling agent is that the compatibilities such as BYK 333 or BYK 042 are good, does not influence the levelling agent of transparency and glossiness.
The defoaming agent is that the compatibilities such as BYK 052, BYK 053 or BYK 056 are good, colorless and transparent polyurethane defoaming agent.
The deicer is zeolite, triethyl orthoformate, ALT 201, ALT 401 or (of light color, the smell of ALT 101 It is low).
The antioxidant is PUR68.
The UV light stabilizing agent is 2- (bis- Ding Shuji phenyl of 2- hydroxyl -3,5-) -5- chlorinated benzotriazole, 2- (2 '-hydroxyls Base -3 ', 5 '-diamyl phenyl) benzotriazole, 2-hydroxy-4-n-octoxybenzophenone, 2- [bis- (the 2,4- dimethylbenzene of 2,4- Base) in -2- (cyanuro 1,3,5) 5- phenol octyloxy and bis- (1,2,2,6,6- pentamethyl -4- piperidyl) sebacates one Kind is several.
The catalyst is dibutyl tin dilaurate, dibutyltin dichloride, dibutyltin diacetate, double morpholine diethyls One or more of base ether, stannous octoate, triethylene diamine, diazabicylo and triethylamine.
The present invention provides a kind of preparation methods of non yellowing polyurethane material for crash dummy, comprising:
(1) 50~95wt% of polyether polyol and 5~50wt% of aliphatic diisocyanate are mixed in 60 DEG C~120 DEG C Aliphatic polyurethane performed polymer is made in reaction；
(2) small molecule amine, polyether polyol are separately added into reaction vessel, in 110 DEG C, pressure≤- 0.095MPa Under the conditions of dehydration to moisture less than 0.05%, be then cooled to 65~70 DEG C of 0.1~5wt% of addition levelling agent, defoaming agent 0.1~ 5wt%, 0.5~5wt% of deicer, 0.2~0.5wt% of antioxidant, 0.2~0.5wt% of UV light stabilizing agent, catalyst 0.1 ~5wt%, stirs evenly, and obtains chain extender；
(3) aliphatic polyurethane performed polymer and chain extender are stirred according to mass ratio 1:0.1~1:0.3, very Sky removes the bubble that stirring generates, and is poured into 60~120 DEG C of mold, by 60~120 minutes, demoulding, then 60~120 At DEG C by 24~36 hours after cure to get.
Beneficial effect
(1) present invention reaches Shao A 55~75 by raw material and formula design, product hardness, appearance be it is colorless and transparent, no Xanthochromia has good resilience, while having good tension, tearing strength, good weatherability, UV resistant, oxytolerant The performances such as change；
(2) present invention employs Pouring form production, simple process does not need special equipment, before having good application Scape.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Embodiment 1
Specific formula
B component NCO%=3.7%.
The preparation method is as follows:
(1) IPDI, GE-210 and GEP-330N are mixed in 110 DEG C of reactions, aliphatic polyurethane performed polymer, i.e. B is made Component；
(2) small molecule amine, GEP-330N, MN-500, DL-400 are separately added into glass beaker, in 110 DEG C, pressure Under conditions of≤- 0.095MPa then dehydration is cooled to 65~70 DEG C of addition levelling agent BYK333, disappears to moisture less than 0.05% Infusion BYK053, antioxidant PUR68, stir evenly, and obtain chain extender, i.e. component A；
(3) aliphatic polyurethane performed polymer and chain extender are stirred according to mass ratio 1:0.1, is removed in vacuum and stirs The bubble for mixing generation is poured into 120 DEG C of mold, by 60 minutes, demoulding, then at 120 DEG C after 24 hours sulphur Change to get non yellowing polyurethane material.
Embodiment 2
Specific formula
B component NCO%=3.7%.
The preparation method is as follows:
(1) IPDI, GE-210 and GEP-330N are mixed in 110 DEG C of reactions, aliphatic polyurethane performed polymer, i.e. B is made Component；
(2) small molecule amine, GEP-330N, MN-500, DL-400 are separately added into glass beaker, 90 DEG C, pressure≤- Under conditions of 0.095MPa then dehydration is cooled to 65~70 DEG C of addition levelling agent BYK333, defoaming to moisture less than 0.05% Agent BYK053, antioxidant PUR68, stir evenly, and obtain chain extender, i.e. component A；
(3) aliphatic polyurethane performed polymer and chain extender are stirred according to mass ratio 1:0.1, is removed in vacuum and stirs The bubble for mixing generation is poured into 120 DEG C of mold, by 60 minutes, demoulding, then at 120 DEG C after 24 hours sulphur Change to get non yellowing polyurethane material.
Recruitment evaluation
Non yellowing polyurethane material test hardness, transparency, mechanical strength, yellowing resistance that Examples 1 and 2 are obtained etc. Physical property and appearance, as shown in the table:
Project Unit Embodiment 1 Embodiment 2 Existing dummy currently on the market
Demould hardness Shore A 70 72 45
Final hardness Shore A 70 72 70
Transparency Light transmittance % 97 97 0
Breaking strength Mpa 21 25 5
Tearing strength KN/m 70 80 21.5
Xanthochromia grade UV grade (for 24 hours) IV IV 0*
* note: material inherently yellow is opaque.

Claims (8)

1. a kind of non yellowing polyurethane material for crash dummy, it is characterised in that: including aliphatic polyurethane performed polymer and Chain extender；Wherein, by mass percentage, the raw material of aliphatic polyurethane performed polymer is polyether polyol 50~95% and aliphatic 5~50wt% of diisocyanate；The raw material of chain extender is small molecule amine 2~10%, polyether polyol 10~90%, other auxiliary agents 0.1~5%.
2. a kind of non yellowing polyurethane material for crash dummy according to claim 1, it is characterised in that: described poly- The molecular weight of ethoxylated polyhydric alcohol is 300~4000, and degree of functionality is 2~4, is selected from GE-210, GE-220A, GE-204, RA-640, NT- One of 403A, DV-125, MN-500, MN-700, MN-1000, MN-1500, MN-3050D, GEP-330N, GE-303 or It is several.
3. a kind of non yellowing polyurethane material for crash dummy according to claim 1, it is characterised in that: the rouge Fat (cyclo) aliphatic diisocyanates are hexamethylene diisocyanate HDI, HDI trimer, HDI biuret, isophorone diisocyanate IPDI, dimethylene dicyclohexane diisocyanate H12One or more of MDI.
4. a kind of non yellowing polyurethane material for crash dummy according to claim 1, it is characterised in that: the rouge Isocyanate index NCO%=1~5% of fat race base polyurethane prepolymer for use as.
5. a kind of non yellowing polyurethane material for crash dummy according to claim 1, it is characterised in that: described small Molecular amine is 3,3 '-two chloro- 4,4 '-diphenylmethanediamiand MOCA, 3,5- dimethythiotoluene diamine DMTDA, 3,5- diethyls Base toluenediamine DETDA, 4,4 '-di-2-ethylhexylphosphine oxides (the chloro- 2,6- diethylaniline of 3-) MCDEA, 4,4 '-di-2-ethylhexylphosphine oxides (2,6- bis- One or more of ethyl) aniline MDEA.
6. a kind of non yellowing polyurethane material for crash dummy according to claim 1, it is characterised in that: it is described its His auxiliary agent include 0.1~5wt% of levelling agent, 0.1~5wt% of defoaming agent, 0.5~5wt% of deicer, antioxidant 0.2~ One or more of 0.5wt%, 0.2~0.5wt% of UV light stabilizing agent, 0.1~5wt% of catalyst.
7. a kind of non yellowing polyurethane material for crash dummy according to claim 6, it is characterised in that: the stream Flat agent is BYK 333 or BYK 042；The defoaming agent is BYK 052, BYK 053 or BYK 056；The deicer be zeolite, Triethyl orthoformate, ALT 201, ALT 401 or ALT 101；The antioxidant is PUR68；The UV light stabilizing agent is 2- (bis- Ding Shuji phenyl of 2- hydroxyl -3,5-) -5- chlorinated benzotriazole, 2- (2 '-hydroxyls -3 ', 5 '-diamyl phenyl) benzo three Azoles, 2-hydroxy-4-n-octoxybenzophenone, 2- [2,4- bis- (2,4- xylyls) -2- (cyanuro 1,3,5) 5- octyloxy One or more of phenol and bis- (1,2,2,6,6- pentamethyl -4- piperidyl) sebacates；The catalyst is two laurels Sour dibutyl tin, dibutyltin dichloride, dibutyltin diacetate, double morpholine Anaesthetie Ethers, stannous octoate, triethylene diamine, One or more of diazabicylo and triethylamine.
8. a kind of preparation method of the non yellowing polyurethane material for crash dummy, comprising:
(1) 50~95wt% of polyether polyol and 5~50wt% of aliphatic diisocyanate are mixed in 60 DEG C~120 DEG C instead It answers, aliphatic polyurethane performed polymer is made；
(2) small molecule amine, polyether polyol are separately added into reaction vessel, in 110 DEG C, pressure≤- 0.095MPa condition It is lower dehydration to moisture less than 0.05%, be then cooled to 65~70 DEG C of 0.1~5wt% of addition levelling agent, defoaming agent 0.1~ 5wt%, 0.5~5wt% of deicer, 0.2~0.5wt% of antioxidant, 0.2~0.5wt% of UV light stabilizing agent, catalyst 0.1 ~5wt%, stirs evenly, and obtains chain extender；
(3) aliphatic polyurethane performed polymer and chain extender are stirred according to mass ratio 1:0.1~1:0.3, vacuum is removed The bubble for going stirring to generate, is poured into 60~120 DEG C of mold, by 60~120 minutes, demoulding, then at 60~120 DEG C By after cure in 24~36 hours to get.
CN201811068088.5A 2018-09-13 2018-09-13 Non-yellowing polyurethane material for crash dummy and preparation method thereof Active CN109438659B (en)

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CN110093138A (en) * 2019-05-28 2019-08-06 广东普赛达密封粘胶有限公司 A kind of color inhibition high-strength polyurethane U.S. seam glue and preparation method thereof
CN111004366A (en) * 2019-12-19 2020-04-14 湖南大学 Tissue organ-imitated polyurethane-based composite material for dummy and preparation method thereof
CN114907547A (en) * 2022-06-27 2022-08-16 福建省军源体育用品有限公司 Self-repairing stabbing and killing training dummy and manufacturing method thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110093138A (en) * 2019-05-28 2019-08-06 广东普赛达密封粘胶有限公司 A kind of color inhibition high-strength polyurethane U.S. seam glue and preparation method thereof
CN111004366A (en) * 2019-12-19 2020-04-14 湖南大学 Tissue organ-imitated polyurethane-based composite material for dummy and preparation method thereof
CN114907547A (en) * 2022-06-27 2022-08-16 福建省军源体育用品有限公司 Self-repairing stabbing and killing training dummy and manufacturing method thereof

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