CN108456294A - A kind of polyurethane elastomer and preparation method thereof that high temperature-resistant grease is ageing-resistant - Google Patents

A kind of polyurethane elastomer and preparation method thereof that high temperature-resistant grease is ageing-resistant Download PDF

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Publication number
CN108456294A
CN108456294A CN201810106821.1A CN201810106821A CN108456294A CN 108456294 A CN108456294 A CN 108456294A CN 201810106821 A CN201810106821 A CN 201810106821A CN 108456294 A CN108456294 A CN 108456294A
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polyurethane elastomer
resistant
diisocyanate
polyurethane
ageing
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CN108456294B (en
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刘锦春
刘晓文
方雅茹
秦贤玉
孙秀利
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Qingdao University of Science and Technology
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Qingdao University of Science and Technology
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Abstract

The present invention relates to a kind of polyurethane elastomer and preparation method thereof that high temperature-resistant grease is ageing-resistant, the polyurethane elastomer component includes：53.59~62.75wt% of polymer polyatomic alcohol, 26.49~31.15wt% of diisocyanate, 2.55~8.78wt% of chain extender, 0.1~3.0wt% of antioxidant, 5.0~20.0wt% of non-polar additives, 0.5~2.0wt% of bulking agent, 0~0.1wt% of catalyst.Preparation method is reacted by polymer polyatomic alcohol, diisocyanate and antioxidant and other auxiliary agents under the conditions of 60~80 DEG C first is made performed polymer, then polyurethane elastomer is made with chain extender reaction under the action of catalyst.The ageing-resistant Mechanical Properties of Polyurethane Elastomers of high temperature-resistant grease obtained by the present invention is good, and hardness adjustable extent is big, and resistance to polarity is oil can be good, and heat aging property is excellent.

Description

A kind of polyurethane elastomer and preparation method thereof that high temperature-resistant grease is ageing-resistant
Technical field
The present invention provides a kind of method for preparing polyurethane elastic body, belong to technical field of polymer materials, specifically relate to And a kind of polyurethane elastomer and preparation method thereof that high temperature-resistant grease is ageing-resistant.
Background technology
Heat resistance of the polyurethane elastomer in inert gas such as nitrogen is fair, and oxytolerant and ozone performance be also very under room temperature It is good, but effect can accelerate the ager process of polyurethane while high temperature and oxygen, make material property is bright to see reduction and influence to use. The temperature upper limit that general polyurethane elastomer is used continuously for a long time in air is 80~90 DEG C, and the short time uses reachable 120 DEG C, be about 130 DEG C on the temperature that thermal oxide shows to significantly affect.
In addition, polyurethane elastomer is a kind of highly polar high molecular material, and it is small with the compatibility of nonpolar mineral oil, it is firing It hardly weathers in material oily (such as kerosene, gasoline) and machinery oil (such as hydraulic oil, machine oil, plain oil), but in polarity Performance loss in fat is larger.
Invention content
The present invention is directed to overcome the defect of above-mentioned oil resistant, heat oxygen aging resistance etc., its purpose is to provide a kind of resistance to height The ageing-resistant polyurethane elastomer and preparation method thereof of warm grease.The present invention is by being added bis sulfone S, bisphenol-A and hydroquinone two The ingredient of the structures containing symmetry rigid such as hydroxyethyl ether (HQEE), by it with other chain extenders and for improving polyurethane elastomer High temperature resistant, the oil energy of resistance to polarity.In addition, the non-polar oils such as paraffin oil, naphthenic oil, which are added, to play one to polar emollient fat Fixed buffer action improves the performance of resistance to polar lipid.
Mechanical Properties of Polyurethane Elastomers produced by the present invention is good, under the conditions of 140 DEG C resistance to polarity it is oil can and it is heat-resisting Ageing properties are excellent.
Technical solution is used by realizing above-mentioned purpose of the present invention：
A kind of polyurethane elastomer that high temperature-resistant grease is ageing-resistant, the polyurethane elastomer is by polymer polyatomic alcohol, two different Cyanate and chain extender are reacted by prepolymer method, cast, demould, vulcanization is made, wherein first by polymer polyatomic alcohol, two Isocyanates and antioxidant reacted under the conditions of 60~80 DEG C be made performed polymer, then under the action of catalyst with chain extender reaction system Polyurethane elastomer is obtained,.
In a kind of polyurethane elastomer that high temperature-resistant grease is ageing-resistant and preparation method thereof, each component is shared in the feed Mass percent is as follows：53.59~62.75wt% of polymer polyatomic alcohol, 26.49~31.15wt% of diisocyanate expand Chain 2.55~8.78wt% of agent, 0.1~3.0wt% of antioxidant, 5.0~20.0wt% of non-polar additives, bulking agent 0.5~ 2.0wt%, 0~0.1wt% of catalyst.
The polymer polyatomic alcohol is that polytetrahydrofuran ether glycol, end hydroxy polyether polyalcohol 330N, common polyether are polynary Alcohol 3600, common polyether polyalcohol 36/28, polyether polyol TEP2400, polyester polyol PDA1000, polycaprolactone polyol One or both of with polycarbonate polyol, the molecular weight of polymer polyatomic alcohol is 1000~6000.
The diisocyanate is 4,4 '-methyl diphenylene diisocyanates (pure MDI, liquefaction modified MDI), 2,4- toluene One or more of diisocyanate (TDI-80, TDI-100) mixture.
The chain extender includes two kinds of chain extender A and chain extender B, and wherein chain extender A is that 2,2- is bis- to phenol propane (bis-phenol A), 4,4- dihydroxydiphenylsulisomers (bis sulfone S), hydroquinone two hydroxy ethyl ether (HQEE)；Chain extender B is 3,5- dimethyl sulphur-based toluene One or more of diamines (DMTDA), 1,4-butanediol (BDO) and trimethylolpropane (TMP) mixture, it is preferably double Sulfone S, BDO and DMTDA one or more mixture.
The antioxidant is 3,5- di-tert-butyl-hydroxy phenyl propionic acid octadecanol esters (1076), four [β-(3,5- bis- Tert-butyl-hydroxy phenyl) propionic acid] one kind in pentaerythritol ester (1010) and phosphorous acid three (2,4- di-tert-butyl-phenyl) ester Or two or more mixtures, preferably 1010.
The non-polar additives are nonpolar oils, are one kind in paraffin oil, naphthenic oil and aromatic naphtha, preferably paraffin Oil, the bulking agent are organic silicone oil.
The catalyst is triethylenediamine (A-33), dibutyltin dilaurate (T-12) and stannous octoate (T- 9) one kind in, preferably T-12.
The present invention also provides a kind of above-mentioned method for preparing polyurethane elastic body that high temperature-resistant grease is ageing-resistant, techniques It is as follows：By 53.59~62.75wt% polymer polyatomic alcohols under the conditions of 100~120 DEG C vacuum dehydration at least 0.5h to bubble-free It generates；Then 26.49~31.15wt% isocyanates, 0.1~3.0wt% antioxidant and 5.0~20.0wt% nonpolarity is added Additive, 0.5~2.0wt% bulking agents, stir evenly, and 1~3h is reacted under the conditions of 80~90 DEG C, vacuum dehydration again, Base polyurethane prepolymer for use as is made；Base polyurethane prepolymer for use as and 2.55~8.78wt% chain extenders is anti-under 0~0.1wt% catalyst It answers, pour into a mould, demould, and the vulcanization 16~for 24 hours under the conditions of 100~140 DEG C, the ageing-resistant elastic polyurethane of high temperature-resistant grease is made Body.Because being related to the uses of the chain extenders such as bis sulfone S, bisphenol-A in the present invention, in view of its exclusive use or with BDO or DMTDA etc. Solubility is low when chain extender mixes, and influences whether the dosage of the chain extenders such as bis sulfone S, bisphenol-A, therefore in the specific implementation in polyalcohol In add above-mentioned bis sulfone S or bisphenol-A to increase its usage amount.
Further, preparation method of the invention is：By 53.59~62.75wt% polymer polyatomic alcohols 100~120 Under the conditions of DEG C vacuum dehydration at least 0.5h to bubble-free generate；Then be added 26.49~31.15wt% isocyanates, 0.1~ 3.0wt% antioxidant and 5.0~20.0wt% non-polar additives, 0.5~2.0wt% chain extenders A, 0.5~2.0wt% increase-volumes Agent stirs evenly, and 1~3h is reacted under the conditions of 80~90 DEG C, and base polyurethane prepolymer for use as is made in vacuum dehydration again；By poly- ammonia Ester performed polymer is reacted under 0~0.1wt% catalyst with 2.05~6.78wt% chain extenders, pours into a mould, is demoulded, and 100~140 Vulcanization 16 under the conditions of DEG C~for 24 hours, the ageing-resistant polyurethane elastomer of high temperature-resistant grease is made.
The advantages of the present invention are：A kind of polyurethane elastomer that high temperature-resistant grease is ageing-resistant is provided, Mechanical property is good, and oil resistant (non-polar oil and polarity grease) performance is good, and heat-resistant air aging property is excellent, and preparation process letter It is single, it is easy to operate.
Description of the drawings
Fig. 1 is the infrared spectrum for the ageing-resistant polyurethane elastomer of high temperature-resistant grease that embodiment 1 is prepared；
Fig. 2 is the thermogravimetric analysis figure for the ageing-resistant polyurethane elastomer of high temperature-resistant grease that embodiment 1 is prepared；
Fig. 3 is the infrared spectrum for the ageing-resistant polyurethane elastomer of high temperature-resistant grease that embodiment 3 is prepared；
Fig. 4 is the thermogravimetric analysis figure for the ageing-resistant polyurethane elastomer of high temperature-resistant grease that embodiment 3 is prepared.
Specific implementation mode
Extraction device of the present invention and method are described in detail below in conjunction with the drawings and specific embodiments, but embodiment is not It should limit the scope of the invention.
A kind of polyurethane elastomer that high temperature-resistant grease is ageing-resistant, specific embodiment are as follows：
Embodiment 1
Respectively by the polyether polyol 330N of polyether polyol PTMG1000,15.89wt% of 37.07wt%, 100~ Under the conditions of 120 DEG C vacuum dehydration at least 0.5h to bubble-free generate；Then be added 30.42wt% MDI, 1.2wt% 1010, 9.47wt% paraffin oils, 1.06wt% bis sulfone S and 1.5wt% silicone oil DC193, stir evenly, and anti-under the conditions of 80~90 DEG C 1~3h is answered, again vacuum dehydration, base polyurethane prepolymer for use as is made；By base polyurethane prepolymer for use as and 2.83wt%BDO and 0.46wt% TMP mix, be added dropwise 0.02wt% T-12 catalysis reaction, later pour into a mould, demould and under the conditions of 100~140 DEG C vulcanization 16~ For 24 hours, a kind of polyurethane elastomer that high temperature-resistant grease is ageing-resistant is made.
Table 1
Embodiment 2
Respectively by the polyether polyol of 35.62wt% 3600, the polyether polyol 330N of 19.55wt%, 100~120 Under the conditions of DEG C vacuum dehydration at least 0.5h to bubble-free generate；Then be added 29.26wt%MDI, 1.74wt% 1076, 8.51wt% paraffin oils, 1.33wt% bis sulfone S and 2.0wt% silicone oil DC193, stir evenly, and anti-under the conditions of 80~90 DEG C 1~3h is answered, again vacuum dehydration, base polyurethane prepolymer for use as is made；By base polyurethane prepolymer for use as and 2.33wt%BDO and 0.49wt% DMTDA is mixed, and the T-9 catalysis reactions of 0.02wt% are added dropwise, pours into a mould, demould later, vulcanization, it is resistance to old that a kind of high temperature-resistant grease is made The polyurethane elastomer of change.
Table 2
Embodiment 3
Respectively by the polycarbonate polyol PCDL1000 of 59.71wt%, vacuum dehydration is extremely under the conditions of 100~120 DEG C Lack 0.5h to bubble-free generation；Then be added the liquefied mdi of 31.14wt%, the 1010 of 1.5wt%, 8.51wt% paraffin oils, 1.33wt% bisphenol-As and 2.0wt% silicone oil DC193, stir evenly, and 1~3h is reacted under the conditions of 80~90 DEG C, again vacuum Base polyurethane prepolymer for use as is made in dehydration；Base polyurethane prepolymer for use as is mixed with 7.47wt%HQEE and 0.72%wt%BDO, is added dropwise The T-12 catalysis reactions of 0.02wt%, pour into a mould, demould, vulcanization, a kind of polyurethane bullet that high temperature-resistant grease is ageing-resistant is made later Property body.
Table 3
Embodiment 4
Respectively by the bis sulfone S of polycaprolactone polyol CP10,9.89wt% of 45.55wt%, in 100~120 DEG C of conditions Lower vacuum dehydration at least 0.5h to bubble-free generate；Then be added 31.51wt% MDI, 1.85wt% 1010,5.54wt% Naphthenic oil and 1.5wt% silicone oil DC193, stir evenly, and 1~3h is reacted under the conditions of 80~90 DEG C, vacuum dehydration again, system Obtain base polyurethane prepolymer for use as；Base polyurethane prepolymer for use as is mixed with 2.54wt%HQEE and 0.69wt%TMP, the A- of 0.02wt% is added dropwise 33 catalysis reactions, pour into a mould, demould, vulcanization, a kind of polyurethane elastomer that high temperature-resistant grease is ageing-resistant is made later.
Table 4
Embodiment 5
Respectively by the bis sulfone S of polyester polyol PDA-1000,2.67wt% of 50.28wt%, in 100~120 DEG C of conditions Lower vacuum dehydration at least 0.5h to bubble-free generate；Then the 1010 of the TDI-80 and 1.8wt% of 31.5wt% are added, 5.82wt% naphthenic oils and 2.0wt% silicone oil DC193, stir evenly, and 1~3h is reacted under the conditions of 80~90 DEG C, again very Sky dehydration, is made base polyurethane prepolymer for use as；Base polyurethane prepolymer for use as is mixed with the bis sulfone S of the DMTDA of 5.52wt% and 0.41wt%, The T-12 catalysis reactions of 0.01wt% are added dropwise, pours into a mould, demould later, vulcanization, a kind of ageing-resistant poly- ammonia of high temperature-resistant grease is made Ester elastomer.
Table 5
Embodiment 6
Respectively by the polymer polyatomic alcohol 36/28 of the polyether polyol TEP-240 and 14.74wt% of 48.72wt%, Under the conditions of 100~120 DEG C vacuum dehydration at least 0.5h to bubble-free generate；Then be added 27.3wt% TDI-100 and The 1010 of 1.8wt%, stir evenly, and 1~3h is reacted under the conditions of 80~90 DEG C, and it is pre- that polyurethane is made in vacuum dehydration again Aggressiveness；Base polyurethane prepolymer for use as is mixed with the bisphenol-A of the BDO of 6.90wt% and 0.54wt%, the T-9 catalysis of 0.01wt% is added dropwise Reaction pours into a mould, demoulds, vulcanization, a kind of polyurethane elastomer that high temperature-resistant grease is ageing-resistant is made later.
Table 6
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc. Imitate embodiment.But it is every without departing from technical solution of the present invention content, according to the technical essence of the invention to above example institute Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.

Claims (9)

1. a kind of polyurethane elastomer, which is characterized in that its component includes in terms of mass percent shared in the feed：Polymerization Object 53.59~62.75wt% of polyalcohol, 26.49~31.15wt% of diisocyanate, 2.55~8.78wt% of chain extender, antioxygen 0.1~3.0wt% of agent, 5.0~20.0wt% of non-polar additives, 0.5~2.0wt% of bulking agent, 0~0.1wt% of catalyst.
2. polyurethane elastomer according to claim 1, which is characterized in that the polymer polyatomic alcohol is PolyTHF Ether glycol, end hydroxy polyether polyalcohol 330N, common polyether polyalcohol 3600, common polyether polyalcohol 36/28, polyether polyol One or both of TEP2400, polyester polyol PDA1000, polycaprolactone polyol and polycarbonate polyol, polymer The molecular weight of polyalcohol is 1000~6000.
3. polyurethane elastomer according to claim 1, which is characterized in that the diisocyanate is 4,4 '-diphenyl One kind in methane diisocyanate (pure MDI, liquefaction modified MDI), 2,4 toluene diisocyanate (TDI-80, TDI-100) Or two or more mixtures, preferably MDI.
4. polyurethane elastomer according to claim 1, which is characterized in that the chain extender is that 2,2- is bis- to phenol propane (bisphenol-A), 4,4- dihydroxydiphenylsulisomers (bis sulfone S), hydroquinone two hydroxy ethyl ether (HQEE), 3,5- dimethythiotoluene diamines (DMTDA), one or more of 1,4-butanediol (BDO) and trimethylolpropane (TMP) mixture, preferably bis sulfone S, BDO and DMTDA one or more mixtures.
5. polyurethane elastomer according to claim 1, which is characterized in that the antioxidant is 3,5- di-t-butyls -4- Hydroxy-phenylpropionic acid octadecanol ester (1076), four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters (1010) and one or more of (2,4- di-tert-butyl-phenyls) ester of phosphorous acid three (168) mixture.
6. polyurethane elastomer according to claim 1, which is characterized in that the catalyst is triethylenediamine (A- 33), one kind in dibutyltin dilaurate (T-12) and stannous octoate (T-9).
7. polyurethane elastomer according to claim 1, which is characterized in that the non-polar additives are nonpolar oils One kind in liquid, such as paraffin oil, naphthenic oil, aromatic naphtha etc., preferred paraffinic oils；The bulking agent is to contain amphiphilic structure Surfactant, including neopelex, tween, silicone oil etc., preferably silicone oil.
8. claim 1-7 any one of them method for preparing polyurethane elastic body, which is characterized in that by polymer polyol Alcohol, diisocyanate and chain extender are reacted by prepolymer method, cast, demould, vulcanization is made, wherein more by polymer first First alcohol, diisocyanate and antioxidant and other auxiliary agents react under the conditions of 60~80 DEG C is made performed polymer, then makees in catalyst Polyurethane elastomer is made with chain extender reaction with lower.
9. method for preparing polyurethane elastic body according to claim 8, which is characterized in that by 53.59~62.75wt% Polymer polyatomic alcohol under the conditions of 100~120 DEG C vacuum dehydration at least 0.5h to bubble-free generate；Then be added 26.49~ 31.15wt% isocyanates, 0.1~3.0wt% antioxidant and 5.0~20.0wt% non-polar additives, 0.5~2.0wt% Bulking agent stirs evenly, and 1~3h is reacted under the conditions of 80~90 DEG C, and base polyurethane prepolymer for use as is made in vacuum dehydration again；It will Base polyurethane prepolymer for use as is reacted under 0~0.1wt% catalyst with 2.55~8.78wt% chain extenders, pours into a mould, is demoulded, and 100 Vulcanization 16 under the conditions of~140 DEG C~for 24 hours, the ageing-resistant polyurethane elastomer of high temperature-resistant grease is made.
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CN109942788A (en) * 2019-02-21 2019-06-28 唯万科技有限公司 Self-lubricating hydrolysis resistant polyurethane elastic material and preparation method thereof
CN110079091A (en) * 2019-03-25 2019-08-02 常州达奥新材料科技有限公司 A kind of preparation method of resistance to ablation composite insulation material
CN112759736A (en) * 2020-12-28 2021-05-07 山东一诺威聚氨酯股份有限公司 High-temperature-resistant polyurethane elastomer and preparation method thereof
CN113831779A (en) * 2021-08-10 2021-12-24 铱格斯曼航空科技集团股份有限公司 Composite wave-absorbing coating and preparation method thereof
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CN105461877A (en) * 2015-12-21 2016-04-06 中国科学院山西煤炭化学研究所 Synthetic method of thermocuring polyurethane elastomer composite material for sealing materials
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Publication number Priority date Publication date Assignee Title
CN109535360A (en) * 2018-11-28 2019-03-29 韶关市合众化工有限公司 A kind of polyarylsulfone (PAS) modified polyurethane resin emulsion
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