CN106317853A - Polyurethane elastomer composition, polyurethane elastomer preparation method and vehicle interior part skin - Google Patents
Polyurethane elastomer composition, polyurethane elastomer preparation method and vehicle interior part skin Download PDFInfo
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- CN106317853A CN106317853A CN201510375086.0A CN201510375086A CN106317853A CN 106317853 A CN106317853 A CN 106317853A CN 201510375086 A CN201510375086 A CN 201510375086A CN 106317853 A CN106317853 A CN 106317853A
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Abstract
The invention relates to a polyurethane elastomer composition which contains a component A and a component B, wherein the component A is polyhydric alcohol and the component B is polyisocyanate, and in parts by weight, the ratio of the component A to the component B is 100/20-300, wherein the polyurethane elastomer composition further contains expanded microspheres; and the viscosity of the component A and/or the component B is from 500 to 10000 mPa.s. The polyurethane elastomer provided by the invention has lower bulk density and lower material cost. Meanwhile, the problem of easy layering of the expandable microspheres in the system can be effectively improved by controlling the viscosity of the components.
Description
Technical field
The present invention relates to a kind of polyurethane elastomeric compositions, elastic polyurethane preparation and the application in terms of automotive upholstery thereof, belong to technical field of polymer preparation.
Background technology
Vehicle interior article safe driving, good driving environment is provided in terms of have very important effect, its inner decoration piece epidermis can be manufactured by multiple material: such as polrvinyl chloride (PVC)
With TPU epidermis (being manufactured by roto casting), TPO epidermis (by vacuum mo(u)lding or roto casting manufacture) and PU epidermis (spraying or reaction injection molding(RIM)).
All there is some shortcoming more or less in the moulding article of these materials.Such as: PVC can discharge two English and chlorinated secondary product when decomposing, and causes environmental pollution.Meanwhile, the problem that the black brittleness of PVC material likely can cause secure context.The Boardy Feeling of TPO goods, sense of touch is uncomfortable, and its surface the most not scratch-resistant.TPU goods are to the good sense of touch of people, but must be manufactured by slush molding method, and energy consumption is relatively big, also has higher requirement to mould.
PU goods receive significant attention due to its comfortable sense of touch and superior performance.General polyurethane industrial commonly uses aromatic isocyanate (such as toluene di-isocyanate(TDI), benzhydryl vulcabond) as firming agent, although having preferable dynamic and wearability, but the weather resisteant of aromatic urethane is poor, it is exposed in air, under the effect of ultraviolet, easily there is xanthochromia, cause hydraulic performance decline.Generally require when as vehicle interior article epidermis and do anti-ultraviolet extra process.
Although aliphatic isocyanate is difficult to xanthochromia, weatherability is preferable, but price is costly, therefore would generally be added into expended microsphere in polyurethane elastomeric compositions and obtain foaming product, on the one hand reduces product density, favourable automotive light weight technology；On the other hand, it is possible to reduce the consumption of aliphatic isocyanate, it is thus achieved that cost advantage.Described expended microsphere is a kind of core-shell polymers microsphere comprising low-boiling compound, and it expands at the rear casing that is heated, the gasification of low-boiling compound that inside comprises, the volumetric expansion of microsphere tens times.But it expands temperature required the highest, time is the longest, if expended microsphere being directly added into thin layer polyurethane product or epidermis, when low-temperature setting, polyurethane component reacts institute's liberated heat often deficiency, so that microsphere expansion or expansion effect are undesirable, to be caused and can not give full play to its performance.
Summary of the invention
For solving the problems referred to above, the invention provides a kind of polyurethane elastomeric compositions, containing component A and B component in described polyurethane elastomeric compositions, wherein, described component A is polyhydric alcohol, and described B component is polyisocyanates, in parts by weight, component A/B component is 100/20 ~ 300；Possibly together with expandable microspheres in described polyurethane elastomeric compositions；The viscosity of described component A and/or B component is 500 ~ 10000mPa.s.
The present invention provide in order to reduce extrudate density to greatest extent, described expended microsphere foamed before being added into system the most in advance, avoid the problem that can not foam in finished product production process or can not fully foam, make final goods can obtain thinner thickness and lower body density, and reduce material cost further.Meanwhile, when being controlled within the specific limits by compositional viscosity, the expended microsphere easy lamination problem in system can be effectively improved.
The present invention also provides for the preparation method of a kind of elastic polyurethane, comprises the steps of:
(1) expandable microspheres is added in component A and/or the B component of above-mentioned polyurethane elastomeric compositions；
(2) component A in step (1) and B component are mixed in proportion obtain react feed liquid；
(3) the reaction feed liquid in step (2) is injected in mould, heats under uniform temperature, the demoulding after curing molding, described polyurethane elastomer.
The present invention also provides for a kind of inner decoration piece epidermis, and described surface uses above-mentioned polyurethane elastomeric compositions to make.Obtained inner decoration piece epidermis thickness can as little as 0.1mm, the most also there is lower body density, meet the demand of automotive light weight technology further.
Detailed description of the invention
Technical scheme relates to a kind of polyurethane elastomeric compositions, containing component A and B component in described polyurethane elastomeric compositions, wherein, described component A is polyhydric alcohol, described B component is polyisocyanates, and in parts by weight, component A/B component is 100/20 ~ 300；Possibly together with expended microsphere in described polyurethane elastomeric compositions, described expended microsphere is expandable microspheres.
Under preferable case, described expended microsphere is expandable microspheres.In order to reduce extrudate density to greatest extent, before expended microsphere is added into component in advance at a temperature of 130 ~ 165 DEG C, heating 20 ~ 60min makes microsphere expansion, effectively prevent and cannot foam in finished product production process or problem that foaming effect is undesirable.
Expended microsphere used in the present invention is a kind of core-shell polymers microsphere, and the shell of described microsphere is high molecular polymer, and described microsphere kernel is Hydrocarbon.Described Hydrocarbon is lower boiling alkane compound.It is heated under its expansion temperature, the shell of microsphere softens, internal Hydrocarbon gasification, makes several to tens times of the volumetric expansion of microsphere, becomes expandable microspheres.Typical such as Sweden Akzo Nobel and the product of pine our company of Japan.
By when expandable microspheres is mixed into reaction system, owing to its density is low, in mixed process, expended microsphere easily floats over reaction system surface, goods upper surface and bottom is caused to have different densities, for improving this lamination, the present inventor is found by great many of experiments, controls the viscosity of component, microsphere layering in system, control further to end properties can be effectively reduced.
Inventor is found through experiments, when at room temperature (25 DEG C) are 500 ~ 10000mPa.s to the viscosity of component A and/or B component, it is possible to improve microsphere lamination problem in component very well；In view of easy construction, preferred viscosity is 800 ~ 6000mPa.S,
More preferably 1000 ~ 3000mPa.S.Described expandable microspheres can be individually added into component A or B component, it is also possible to is simultaneously introduced in component A and B component, as long as the viscosity of its added component controls in above-mentioned level.
In the present invention, in terms of polyurethane elastomeric compositions gross weight, the addition of described expended microsphere is 0.01 ~ 10wt%, preferably 0.5 ~ 5wt%, most preferably 1 ~ 2.5wt%.
In one embodiment of the invention, the isocyanate index of described polyurethane elastomeric compositions is 0.80 ~ 1.30, preferably 0.90 ~ 1.20, more preferably 1.00 ~ 1.10.Described isocyanate index is in B component-NCO content and the molar ratio of active hydrogen group content in component A；Described active hydrogen group is that the group that can react with isocyanates, such as hydroxyl, amino containing reactive hydrogen atom.
Described component A polyhydric alcohol is one or more in the hydroxy-end capped performed polymer that PEPA, polyether polyol, polymer polyatomic alcohol, polytetrahydrofuran polyol (PTMEG) or PEPA, polyether polyol, polymer polyatomic alcohol, polytetrahydrofuran polyol (PTMEG) and isocyanates are formed.The performed polymer that generally polyhydric alcohol and isocyanates are formed has hydroxy-end capped and that-NCO blocks two classes, and component A can not be the performed polymer of-NCO end-blocking herein.
The polyhydric alcohol of described component A preferably has the molecular weight of 750-10000, and preferred scope is 1000-5000, most preferably in the range of 1000-4000；The hydroxy functionality of polyhydric alcohol is preferably 2-6, and preferred scope is 2-3.
Under preferable case, possibly together with cahin extension agent, catalyst in described component A.
In the present invention, possibly together with other auxiliary agents in described component A, other auxiliary agents described are antioxidant, plasticizer, UV absorbent, one or more in surfactant, fire retardant and filler；Above-mentioned auxiliary agent can add according to actual needs, the regulation anti-flammability of goods, hardness, density etc., moreover it is possible to improve processing characteristics and non-oxidizability etc. further.
In terms of the gross weight of component A, the performed polymer content of described polyhydric alcohol or hydroxy-end capped polyhydric alcohol is 30wt% ~ 70wt%, and described cahin extension agent content is 1wt% ~ 20wt%, and described catalyst content is 0.01wt% ~ 2wt%, and the content of other auxiliary agents is 0.01wt% ~ 50wt%..
In the present invention, described B component contains the performed polymer of non-aromatic isocyanates and/or non-aromatic isocyanates and polyhydric alcohol.Described non-aromatic isocyanates is without aromatic ring, or its-polyisocyanates that is the most directly connected with aromatic ring of NCO group.Due to the polyurethane containing aromatic isocyanate, illumination, air effect under, be susceptible to xanthochromia, cause hydraulic performance decline；And when using aliphatic isocyanate, do not change, its weather resistance can be greatly improved.
The non-aromatic polyisocyanates that can use has: one or more in hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenation benzhydryl vulcabond (HMDI), phenylenedimethylidyne isocyanates (TXDI), cyclohexyl diisocyanate, tetramethyl xylylene diisocyanate (TMXDIs).
Described catalyst is catalysts for polyurethanes, and described catalysts for polyurethanes is one or more in organometallic catalysts, organoboron catalyst, organic amine catalyst, imidazoles catalyst, quaternary ammonium salt catalyst；Described organometallic catalysts is one or more in organotin catalysts, organolead catalysts, organic mercury catalyst, organic bismuth catalyst, organozinc catalyst.
Described catalyst is one or more in organotin catalysts, organic bismuth catalyst, organozinc catalyst or organic amine catalyst, quaternary ammonium salt catalyst.
The active group Han at least two in described cahin extension agent, described active group is one or more in-OH ,-NH2 ,-NH.Specifically can select ethylene glycol, 1, ammediol, 1, 2-propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, ethylenediamine, butanediamine, propane diamine, hexamethylene diamine, N, N '-dimethyl ethylenediamine, N, N '-dimethyl butanediamine, isophorone diamine, hydrogenation benzhydryl diamidogen (HMDA), cyclohexanediamine, polyetheramine, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, dihydroxy methylpropane, trimethylolpropane, bisphenol-A, hydrogenated bisphenol A, one or more in the Polyethylene Glycol (Weight-average molecular is 100-400) of low-molecular-weight.
Described cahin extension agent, in terms of the gross weight of polyurethane elastomeric compositions, the consumption of described cahin extension agent is 0.01 ~ 20wt%, preferably 5 ~ 15wt%, more preferably 7 ~ 12wt%.
Present invention also offers a kind of method for preparing polyurethane elastic body, comprise the steps:
(1) expandable microspheres is added in component A and/or the B component of above-mentioned polyurethane elastomeric compositions；
(2) component A in step (2) and B component are mixed in proportion obtain react feed liquid；
(3) the reaction feed liquid in step (1) is injected in mould, heats under uniform temperature, the demoulding after curing molding, described polyurethane elastomer.
In above-mentioned method for preparing polyurethane elastic body, the temperature in step (2) is 80 ~ 100 DEG C.
It addition, all right directly once molding on core of above-mentioned polyurethane elastomer, only need to place core in the mould of step (2) in advance, the reaction feed liquid in (1) be injected in mould, the demoulding after curing molding.
Described polyurethane elastomer generally uses the method for RIM reaction injection molding to obtain.
Present invention also offers a kind of automotive upholstery epidermis, epidermis is made up of preceding claim polyurethane elastomeric compositions.Described epidermal thickness is 0.1 ~ 3mm, preferably 0.5 ~ 2.5mm, more preferably 1.0 ~ 2.0mm.
Below in conjunction with embodiment, the present invention is further described in detail, but is not limited to this.
All raw materials in heretofore described embodiment are the most non-to be refered in particular to, and is commercially available prod.
Embodiment
1~4
Polyhydric alcohol in component A contains one or more in A1 ~ A4:
A1: two ethylene oxide-capped functional group's polyether polyol, molecular weight 4000, hydroxyl value 28mgKOH/g.
A2: ethylene oxide-capped trifunctional polyether polyol, molecular weight 5000, hydroxyl value 33.6mgKOH/g.
A3: two ethylene oxide-capped functional group's polyether polyol, molecular weight 2000, hydroxyl value 56mgKOH/g.
A4: three-functionality-degree propylene oxide polyether polyhydric alcohol, molecular weight 3000, hydroxyl value 56mgKOH/g.
The performed polymer of A5:-OH end-blocking adds the ethylene oxide-capped polyether Glycols (molecular weight 4000) of 1000g and the hexamethylene diisocyanate (HDI) of 21g in the reactor of full nitrogen, after mix homogeneously, it is heated to 80 degrees Celsius of reactions, the hydroxyl value of detection reaction system, until stopping heating, cooling after reaching the hydroxyl value content of design, add 30g expandable microspheres, mix homogeneously, vacuum outgas.Hydroxyl value: 13.3mgKOH/g
In addition to above-mentioned A1 ~ A5 polyhydric alcohol, possibly together with one or more in cahin extension agent, catalyst, fire retardant, ultraviolet absorber, antioxidant in component A.
B1: add the propylene oxide polyether polyhydric alcohol (molecular weight 4000) of the low-unsaturation-degree of 1000g and the hydrogenated diphenyl methane diisocyanate (HMDI) of 1200g in the reactor of full nitrogen, after mix homogeneously, it is heated to 90 degrees Celsius of reactions, detection reaction system-NCO content, until reach design-NCO content after stop heating, cooling, add 50g expandable microspheres, mix homogeneously, vacuum outgas.-NCO content: 16.1%.
B2: add ethylene oxide-capped two functional group's polyether polyol (molecular weight 2000) of 1000g and the isophorone diisocyanate (IPDI) of 1100g in the reactor of full nitrogen, after mix homogeneously, it is heated to 95 degrees Celsius of reactions, detection reaction system-NCO content, until reach design-NCO content after stop heating, cooling.Add 50g mass parts expandable microspheres, mix homogeneously, vacuum outgas.-NCO content: 17.3%.
B3: add the trifunctional polyoxypropylene polyol (molecular weight 3000) of 333g, ethylene oxide-capped two functional group's polyether polyol (molecular weight 2000) of 667g, the hexamethylene diisocyanate (HDI) of 700g in the reactor of full nitrogen.After mix homogeneously, be heated to 85 degrees Celsius of reactions, detection reaction system-NCO content, until it reaches design-NCO content after stop heating, cooling.Add 40g expandable microspheres, mix homogeneously vacuum outgas.-NCO content: 17.6%.
B4: add the trifunctional polyoxypropylene polyol (molecular weight 5000) of 333g, ethylene oxide-capped two functional group's polyether polyol (molecular weight 2000) of 667g, the isophorone diisocyanate (IPDI) of 1150g in the reactor of full nitrogen.After mix homogeneously, be heated to 100 degrees Celsius of reactions, detection reaction system-NCO content, until it reaches design-NCO content after stop heating, cooling adds 50g mass parts expandable microspheres, mix homogeneously, vacuum outgas.-NCO content: 18%.
Comparative example
1
Removing used expended microsphere in comparative example 1 without foaming in advance, remaining component and consumption are the most same as in Example 1.
Comparative example
2
By the trifunctional polyoxypropylene polyol (molecular weight 3000) of 333g, 667g ethylene oxide-capped two functional group's polyether polyol (molecular weight 2000) mix homogeneously after, add 30g expandable microspheres, stirring, viscosity is 400mPa.s.Discovery is difficult to mix homogeneously, and after standing a few minutes, microsphere i.e. floats layering, does not carries out next step and operates.
In embodiment 1 ~ 5, component see table 1:
The component proportion of polyurethane elastomer described in table 1 embodiment 1 ~ 5 and comparative example 1
* every component (pbw) in parts by weight；Material temperature 45 DEG C；Mould temperature: 80 DEG C；Injection pressure: 15MPa；The demoulding time: 5 minutes.
Performance test:
The polyurethane elastomer sample prepared in embodiment 1 ~ 5 and comparative example 2 is tested as follows:
1, tensile property test: " GB/T 1040-92 plastic tensile method for testing performance " is tested.
2, hardness test: " GB/T 2411-2008 plastics shore hardness test method " tests.
3, body density: weigh weight m(g of the sample of certain volume), measure the length (l) of taken sample, wide (w), high (h) (cm), its density (ρ) is calculated as follows: ρ=m/ (lXwXh) (g/cm3)。
Test result is as shown in table 2
The test result of sample in table 2 embodiment 1 ~ 5 and comparative example 1
From above-mentioned test result, changing the feed postition of microsphere, well solving microsphere can not adequately expanded problem；The viscosity of regulation and control component can make the compatibility of expandable microspheres and resin be improved.Adding after expandable microspheres, the density of product is significantly shown in reduction.
Obviously, above-described embodiment is only for clearly demonstrating example, and not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also cannot all of embodiment be given exhaustive, and the obvious change thus extended out or variation still in the invention scope of the claims among.
Claims (14)
1. a polyurethane elastomeric compositions, it is characterised in that described polyurethane elastomeric compositions contains component A and B component, and wherein, described component A is polyhydric alcohol, and described B component is polyisocyanates, and in parts by weight, component A/B component is 100/20 ~ 300；Possibly together with expended microsphere in described polyurethane elastomeric compositions, described expended microsphere is expandable microspheres；The viscosity of described component A and/or B component is 500 ~ 10000mPa.s.
Polyurethane elastomeric compositions the most according to claim 1, it is characterised in that in terms of the gross weight of polyurethane elastomeric compositions, the consumption of described expended microsphere is 0.01 ~ 10wt%.
Polyurethane elastomeric compositions the most according to claim 1, it is characterised in that the isocyanate index of described polyurethane elastomeric compositions is 0.80 ~ 1.30.
Polyurethane elastomeric compositions the most according to claim 1, it is characterized in that, described component A polyhydric alcohol is one or more in the hydroxy-end capped performed polymer that PEPA, polyether polyol, polymer polyatomic alcohol, polytetrahydrofuran polyol (PTMEG) or PEPA, polyether polyol, polymer polyatomic alcohol, polytetrahydrofuran polyol (PTMEG) and isocyanates are formed.
Polyurethane elastomeric compositions the most according to claim 1, it is characterised in that possibly together with cahin extension agent and/or catalyst in described component A.
Polyurethane elastomeric compositions the most according to claim 5, it is characterised in that possibly together with other auxiliary agents in described component A, other auxiliary agents described are antioxidant, plasticizer, UV absorbent, one or more in surfactant, fire retardant and filler.
Polyurethane elastomeric compositions the most according to claim 6, it is characterized in that, in terms of component A gross weight, the content of described polyhydric alcohol is 30wt%～80wt%, the content of cahin extension agent is 1wt%～20wt%, the content of catalyst is 0.01wt%～2wt%, and the content of other auxiliary agents is 0.01wt% ~ 50wt%.
Polyurethane elastomeric compositions the most according to claim 1, it is characterised in that contain the performed polymer of non-aromatic isocyanates and/or non-aromatic isocyanates and polyhydric alcohol in described B component.
Polyurethane elastomeric compositions the most according to claim 8, it is characterized in that, described non-aromatic polyisocyanates is one or more in hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenation benzhydryl vulcabond (HMDI), phenylenedimethylidyne isocyanates (TXDI), cyclohexyl diisocyanate, tetramethyl xylylene diisocyanate (TMXDIs).
Polyurethane elastomeric compositions the most according to claim 5, it is characterized in that, described catalyst is catalysts for polyurethanes, and described catalysts for polyurethanes is one or more in organometallic catalysts, organoboron catalyst, organic amine catalyst, imidazoles catalyst, quaternary ammonium salt catalyst.
11. polyurethane elastomeric compositions according to claim 5, it is characterised in that the active group Han at least two in described cahin extension agent, described active group is-OH ,-NH2, one or more in-NH.
12. 1 kinds of method for preparing polyurethane elastic body, it is characterised in that comprise the steps:
(1) expandable microspheres is added in component A and/or the B component of arbitrary described polyurethane elastomeric compositions in claim 1 ~ 11；
(2) component A in step (1) and B component are mixed in proportion obtain react feed liquid；
(3) the reaction feed liquid in step (2) is injected in mould, heats under uniform temperature, the demoulding after curing molding, described polyurethane elastomer.
13. 1 kinds of automotive upholstery epidermises, it is characterised in that described epidermis is made up of described polyurethane reaction system polyurethane elastic composition arbitrary in claim 1 ~ 11.
14. automotive upholstery epidermises according to claim 13, it is characterised in that described epidermal thickness is 0.1 ~ 3mm.
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| WO2020163981A1 (en) * | 2019-02-11 | 2020-08-20 | Dow Global Technologies Llc | Fire resistant polyurethane coating composition and a fire-resistant product comprising the same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110330880A (en) * | 2019-06-27 | 2019-10-15 | 青岛爱尔家佳新材料股份有限公司 | A kind of anticorrosive paint, preparation method and application method |
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