CN101591420B - Spraying plastic polyurethane composition as well as preparation method and application thereof - Google Patents
Spraying plastic polyurethane composition as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a spraying plastic polyurethane composition comprising a polyalcohol component A and an isocyanate performed polymer component B, wherein the component A is polyalcohol mixture comprising the following components in parts by weight: 100 parts of polyalcohol, 5-30 parts of chain extender, 1.5-3.5 parts of non-volatile catalyst, 0.05-5 parts of reactive antifoaming agent and0-5 parts of color paste; the component B is an isocyanate performed polymer formed by the polyreaction of methyl diphenylene diisocyanate and the polyalcohol with the molecular weight of 1000 to 8000 according to a ratio by weight of 100: (5 to 80), and the NCO content is 15-30 percent by weight; and the component A and the component B are separately stored and are matched according to the ratioby weight of 100:30 to 100:110 when in use. The invention discloses a preparation method of the spraying plastic polyurethane composition and an application thereof in manufacturing interior decorations of vehicles.
Description
Technical field
The present invention relates to a kind of plastic-blasting polyurethane composition, its preparation method and the application in making automotive upholstery thereof.
Background technology
Along with popularizing of automobile, the driver is to the automotive interior configuration and decorate, especially the requirement of inside gadget sense organ comfort level is more and more higher.Simultaneously, the trend of the deep and automobile lightness of health environment-friendly theory has also proposed higher standard to automobile-used material.In addition, the processibility of automobile component production and economy also are that automotive industry will be badly in need of improved aspect from now on.This just requires, and scientific workers develop more the multimass excellence, cost is low, workability is strong, the polymer novel material of health environment-friendly.
Automotive upholstery mainly refers to dashboard, bearing circle, sun visor and door-plate, handrail etc., the appearance of these component all contains or partly contains the hard plastic material of leather substance or injection moulding, such as polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymer (ABS), urethane (PU) leather.The moulding of these leathers adopts vacuum to inhale the post forming of mould technology basically.All contain various softening agent to some extent in PVC, the ABS that uses, the PU leather at present, such as, dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DOB), epoxy soybean wet goods.These materials are chemically inert materials, have transport property, therefore, healthy and environment are had potential hazard.In addition, there is the drawback that working (machining) efficiency is low, air contaminative and high energy consumption are arranged in above-mentioned these materials in process of production, such as, their machine-shaping temperature is usually more than 120 ℃; And the PU leather in process of production, need to use solvent as shaping medium, and the recycling of solvent also will consume the more energy, and the volatility of solvent also is conspicuous to the harm of environment; Moreover, when above-mentioned leather substance is used to make automotive upholstery, carry out post formings such as vacuum forming, cause the waste of the energy and the scrap stock of material own and the environmental problem of bringing.
At present, urethane and polyurethane-urea material more and more cause the concern of industry, and the spraying technology of urethane and polyurethane-urea has also obtained significant progress.Such as, at United States Patent (USP) 5,192,594,5,233,009,5,275,888 and document such as Application No. US20050075450 in set forth the spraying technology of urethane and polyurethane-urea.
United States Patent (USP) 5,192,584 have described the structural support body of a kind of polyurethane-urea that is sprayed on the body surface, and the composition of this polyurethane-urea includes special polyol blends, organic diamine, water-retaining agent, silicone antifoam agent and isocyanate component.
United States Patent (USP) 5,233, the polyurethane-urea spray composition in 009 and 5,275,888 be at United States Patent (USP) 5,192, increased filler component on the basis of the basal component in 584, as pipeline, the coating on bathtub surface and the coating of Ceramic glaze.
Described a kind of optical fiber enhanced urethane constituent among the Application No. US20050075450, this constituent is made up of hydrophobic polyol component and isocyanic ester performed polymer component.Owing to contain the above compound of 5 functional groups in the component, so be suitable as gel coating and model resin.Because its low volatility also can be used for ship outer casing etc.
At United States Patent (USP) 5,856, the urethane of a kind of sandwich (interlayer) structure has been described in 371, that is, contain the urethane that one deck do not foam and the urethane of one deck foaming at least.In the layer of polyurethane that does not foam, contain the mica of 10-55%.The polyether glycol and isocyano (NCO) content that comprise hydroxyl value 250-400 in the composition of urethane are the isocyanic ester performed polymer of 20-30wt%.Isocyanate index during two component reaction is 90-130, and whipping agent is optional.
Application No. US20080071058 has described a kind of spray polyurethane-urea material that contains the soft silk structure, and this material is made up of two-pack.Owing to introduced the soft silk structure,, be used for making the material of the sandwich structure that contains one deck non-foaming polyurethane and one deck polyurathamc at least so improved impact resistance.
Yet the described urethane of above-mentioned patent documentation and polyurethane-urea material and spraying technology thereof only can for example as silane coupling agent, coating, sandwich (interlayer) material, and can not be applied to automobile interior trim as the epidermis of leather character as general application.In the composition that wherein has,, can't satisfy the requirement of automotive upholstery condensed components and atomization owing to used silicone antifoam agent, non-reacted catalyzer.
Summary of the invention
Therefore, purpose of the present invention just is to overcome the defective that existing automotive interior material lacks leather texture and environmental protection, thereby provide a kind of plastic-blasting polyurethane composition of forming by the mixture and the isocyanic ester performed polymer of polyvalent alcohol, with its method moulding on die surface, prepare the epidermis of the automotive upholstery of Any shape by spraying.
Another object of the present invention is to provide a kind of preparation method who prepares above-mentioned plastic-blasting polyurethane composition.
A further object of the present invention is to provide above-mentioned plastic-blasting polyurethane composition to be used to prepare the application of automotive upholstery.
For achieving the above object, the present invention adopts following technical scheme:
A kind of plastic-blasting polyurethane composition, it comprises polyol blends component A and modified isocyanate B component, wherein,
Component A is a polyol blends, and it is counted by weight and comprises: reactive defoamer of the chainextender of 100 parts polyvalent alcohol, 5-30 part, the non-volatility catalyzer of 1.5-3.5 part, 0.05-5 part and the toning mill base of 0-5 part;
B component is the isocyanic ester performed polymer, and the polyvalent alcohol that by diphenylmethanediisocyanate and molecular weight is 1000-8000 is by weight 100: 5-80 carries out polyreaction and gets, and its NCO content is 15-30wt%;
Component A and B component are deposited separately, during use by component A: B component equals 100: 30-100: 110 weight ratio is used.
When this urethane carries out the plastic-blasting moulding, by component A and B component by 100: 30-100: 110 weight ratio evenly is sprayed on die surface after mixing through the shower nozzle of the shower nozzle of band static mixer or band high pressure bump mixing tank, component A and B component are carried out the rapid polymerization reaction at die surface immediately, form the plastic-blasting polyurethane material of leather texture.
A kind of preparation method who prepares above-mentioned plastic-blasting polyurethane composition, it comprises the steps:
(1) preparation of component A:
1. the defoamer of preparation feedback: alkali metal hydroxide or bimetal complexes with the 1-50 weight part are catalyzer, at least a low-molecular-weight polyvalent alcohol of 100 weight parts and the propylene oxide and/or the oxyethane of 900-10000 weight part are carried out ring-opening polymerization, then the multipolymer that obtains is made with extra care, filtered, obtaining hydroxyl value is the reactive defoamer of 28-230mgKOH/g;
2. form polyol blends: at least a polyvalent alcohol of 100 weight parts, at least a chainextender of 5-30 weight part, at least a non-volatility catalyzer of 1.5-3.5 weight part, the above-mentioned reactive defoamer of 0.05-5 weight part and the toning mill base of 0-5 weight part are mixed, thermal dehydration under 80～150 ℃ temperature, get polyol blends, sealing is deposited;
(2) preparation of isocyanic ester performed polymer B component:
One or more diphenylmethanediisocyanates are preheated to 40-60 ℃, by MDI: polyvalent alcohol equals 100: the weight ratio of 5-80, the molecular weight that adds through processed is the polyvalent alcohol of 1000-8000, reacted 1-10 hour down at 50-100 ℃, get the isocyanic ester performed polymer of NCO content 15-30wt%, sealing is deposited.
The using method of above-mentioned plastic-blasting polyurethane composition is:
Component A and B component are placed A, the B batch can of spraying equipment respectively, keep the material temperature at 15-60 ℃, in component A: B component is 100: 30-100: the ratio of 110 (weight ratios) evenly is sprayed on die surface, 20-80 is after second, from mould, take out, promptly obtain the plastic-blasting urethane of leather character.
Adopt technical scheme of the present invention, prepared polyurethane surface leatherware has leather character.Compare with the automotive upholstery skin material of prior art, plastic-blasting polyurethane composition of the present invention does not contain any chemically inert materials such as solvent, softening agent and silicone antifoam agent that environmental protection harm is arranged, thereby has avoided this class material because of the water pollution and the atmospheric pollution of moving and volatilization brings; Because of not adopting 3,3 '-two chloro-4,4 '-diamino-ditan (mocha) is made chainextender, the Health hazard risk of also having avoided mocha to bring.Simultaneously, the plastic-blasting urethane of spray mo(u)lding prepared of the present invention does not need through secondary forming process, therefore to have energy-conservation, consumption reduction and reduces the waste of the leftover bits of material own.In addition, it also has higher mechanical strength, curing speed and extremely low advantages such as coagulable component faster.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.Should be understood that following examples only to be used to the present invention is described and be not used in the scope of the present invention that limits.
Plastic-blasting polyurethane composition of the present invention is a two-component composition, and it comprises polyol component A and two kinds of constituents of isocyanic ester performed polymer B component.
The composition of component A and preparation
Reactive defoamer
For the epidermis compactness that increases plastic-blasting urethane or improve its density, need in advance synthetic a kind of reactive defoamer that meets the automotive upholstery environmental requirement.This defoamer is owing to contain hydroxyl, in polymerization process, can be further and the isocyanic ester prepolymer reaction, and become a segmented structure in the polyether polyols with reduced unsaturation structure, therefore can not migrate to material surface.
Reactive defoamer raw material among the component A comprises at least: the alkali metal hydroxide or the duplex metal complexes catalyst of a kind of low molecular polyvalent alcohol of 100 weight parts, the propylene oxide of 900-10000 weight part and/or oxyethane, 1-50 weight part.
Wherein, the content of optimization ethylene oxide structural unit in multipolymer is greater than 50wt%, and more preferably greater than 70wt%, hydroxyl value is 28-230mgKOH/g.
Preferential used alkali metal hydroxide is potassium hydroxide, sodium hydroxide, cesium hydroxide, more preferably potassium hydroxide.
Preferred used bimetal complexes is that six cyanogen close cobalt acid zinc.
Be at least a kind of in glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Xylitol, sorbyl alcohol or the sucrose as the low-molecular-weight polyvalent alcohol of initiator.
On the other hand, reactive defoamer preparation can be adopted ring-opening polymerization method well-known to those skilled in the art, (Xu Peilin etc. write such as " polyurethane material handbook: chapter 4 organic multicomponent alkoxide polymer ", Chemical Industry Press's material and scientific publication center, first version, 2002, P62-66) the related preparation technology of Jie Shaoing.
Particularly, its preparation method comprises: closing cobalt acid zinc with alkali metal hydroxide such as potassium hydroxide or six cyanogen is catalyzer, at least a low-molecular-weight polyvalent alcohol and propylene oxide and/or oxyethane are carried out ring-opening polymerization, then the multipolymer that obtains is made with extra care, filtered, obtaining hydroxyl value is the reactive defoamer of 28-230mgKOH/g.
In the above-mentioned reaction, preferably use two kinds of open loop reagent of propylene oxide and oxyethane, more preferably use propylene oxide to carry out ring-opening polymerization earlier, and then in reaction mixture, add the further ring-opening polymerization of oxyethane.Preferred used propylene oxide structural unit and the weight ratio of ethylene oxide structure unit in multipolymer are 0: 100.
In the above-mentioned defoamer preparation, with low-molecular-weight polyvalent alcohol is initiator, earlier and propylene oxide under the pressure of 0.2-0.6MPa, heat and carry out ring-opening polymerization to polymerization pressure and return zero, adding oxyethane again heats further ring-opening polymerization to polymerization pressure and returns zero under the pressure of 0.2-0.6MPa, to obtain the multipolymer that hydroxyl value is 28-230mgKOH/g, be reactive defoamer through the multipolymer after making with extra care, filtering.
Above-mentioned treating process comprises: distilled water wash, dealkalize, decolouring, dehydration, filtration.Wherein dealkalize and decolouring are preferably with acidic white earth heat treated under nitrogen protection.
80～140 ℃ of preferable polymerization temperature, more preferably 100-120 ℃.
The hydroxyl value of preferred gained multipolymer is 28-230mgKOH/g, more preferably 30-200mgKOH/g.
Polyol blends
As one of component of plastic-blasting polyurethane composition of the present invention, component A is a polyol blends, comprises at least: polyvalent alcohol, chainextender, non-volatility catalyzer, reactive defoamer and toning mill base.
As polyurethane composition of the present invention, polyol blends is counted at least by weight and is comprised among the component A: above-mentioned reactive defoamer of the chainextender of the polyvalent alcohol of 100 parts of molecular weight 1000-8000,5-30 part, the non-volatility catalyzer of 1.5-3.5 part, 0.05-5 part and the toning mill base of 0-5 part.
Among the said components A, described polyvalent alcohol be selected from down the group at least a: polyoxytrimethylene ether trivalent alcohol (trade(brand)name: GEP-330N, molecular weight: 5000; Trade(brand)name: GEP-360N, 8000), polyoxytrimethylene ether dibasic alcohol (trade(brand)name: GEP-2028 molecular weight:, 4000), PTMG dibasic alcohol (trade(brand)name: PTMG-1000 molecular weight:, 1000), polycaprolactone dibasic alcohol (trade(brand)name: P-210 molecular weight:, 1000), PCDL (trade(brand)name: ST-602, molecular weight: 2000) molecular weight:.
Chainextender among the said components A be selected from down at least the group in a kind of: ethylene glycol (EG), 1, ammediol (PG), 1,4-butyleneglycol (BDO), 1,6-hexylene glycol (HG), Resorcinol-two (beta-hydroxyethyl) ether (trade(brand)name: HQEE), diglycol phthalate (trade(brand)name: STEPANPOL
PS-3152), diethyl toluene diamine (trade(brand)name: Ethacure-100), 3,5-diformazan sulfenyl tolylene diamine (trade(brand)name: Ethacure-300), quadrol (EDA), 1,4-butanediamine (BDA), 1,6-hexanediamine (HAD), 4,4 '-methylene-bis (2, the 6-diethyl cyclohexylamine) (M-DECA), 4,4 '-methylene-bis (2-ethyl-6-methyl cyclohexylamine) (M-MECA), isophorone diamine (IPDA).
Non-volatility catalyzer among the said components A can be selected from down the group at least a: amine catalyst (trade(brand)name: NIAX
EF-600), postpone amine catalyst (trade(brand)name: NIAX
EF-602), tin catalyst (trade(brand)name: Fomrez
UL-1, Fomrez
UL-32).
For the color that makes the polyurethane surface after the spraying coating process polymerization is coordinated mutually with the color of interior, or for increasing the color purpose, the toning mill base that can also comprise the 0-5 weight part among the said components A, the toning mill base that preferably comprises the 2-5 weight part is used to adjust the urethane epidermis to needed color.This toning mill base can use present technique field pigment color commonly used, can select commodity to be called BOMEX such as the colour of camel's hair
The mill base of PA-1/0016.
Such as, component A counts by weight and can comprise:
Polyoxytrimethylene ether trivalent alcohol (trade(brand)name: GEP-330N; Molecular weight: 5000), 0-100 part;
Polyoxytrimethylene ether trivalent alcohol (trade(brand)name: GEP-360N; Molecular weight: 300), 0-100 part;
Polyoxytrimethylene ether dibasic alcohol (trade(brand)name: GEP-2028; Molecular weight: 4000), 0-30 part;
Polytetrahydrofuran dibasic alcohol (trade(brand)name: PTMG-1000; Molecular weight: 1000), 0-20 part;
Polycaprolactone dibasic alcohol (trade(brand)name: P-210; Molecular weight: 1000), 0-20 part;
PCDL (trade(brand)name: ST-602, molecular weight: 2000), 0-20 part;
Chainextender, 5-30 part;
The non-volatility catalyzer, 1.5-3.5 part;
Reactive defoamer, 0.05-5 part;
The toning mill base, 2-5 part.
On the other hand, the compound method of this polyol blends is: polyvalent alcohol, chainextender, non-volatility catalyzer, reactive defoamer and toning mill base are mixed according to required weight ratio, and heat, dewater.
In the above-mentioned mixing, preferably with 80～150 ℃ of mixture heating up, more preferably 90-110 ℃.
For the density of avoiding component A internal moisture to influence the plastic-blasting polyurethane material influences the mechanical property of material then, need carry out processed to component A, pack after 2 hours such as mixture being vacuumized dehydration.
The composition of B component and preparation
As another component in the plastic-blasting polyurethane composition of the present invention, B component comprises by weight at least: one or more diphenylmethanediisocyanates (MDI) of 100 parts and one or more molecular weight of 3-80 part are the isocyanic ester performed polymer that produces through polyreaction of the polyol blends of 1000-8000 or the mixture of several performed polymers.
The diphenylmethanediisocyanate (MDI) that is used to form isocyanic ester performed polymer B component be selected from down the group at least a: 4,4 '-diphenylmethanediisocyanate, 2,4-diphenylmethanediisocyanate, carbodiimide diphenylmethanediisocyanate and several mixture in the middle of them.
Such as, diphenylmethanediisocyanate can be: 4, and 4 '-diphenylmethanediisocyanate (trade(brand)name: SUPRASEC
1810), 2,4-diphenylmethanediisocyanate (trade(brand)name: SUPRASEC
3056), carbodiimide diphenylmethanediisocyanate (trade(brand)name: SUPRASEC
2020).
The polyvalent alcohol molecular weight that is used to form isocyanic ester performed polymer B component is 1000-8000, be selected from down the group at least a: polyether glycol, polyester polyol or their several mixtures.
Such as, polyether glycol can be: polyoxytrimethylene ether trivalent alcohol (trade(brand)name: GEP-330N, molecular weight: 5000; Trade(brand)name: GEP-360N, 8000), polyoxytrimethylene ether dibasic alcohol (trade(brand)name: GEP-2028, molecular weight: 4000), PTMG dibasic alcohol (trade(brand)name: PTMG-1000, molecular weight: 1000) molecular weight:;
For another example, polyester polyol can be: adipate polyester polyvalent alcohol (trade(brand)name: L-144, molecular weight 1000; Trade(brand)name: L-244,2000), benzoic anhydride polyester polyol (trade(brand)name: STEPANPOL molecular weight:
PD-56LV, 2000), polycaprolactone dibasic alcohol (trade(brand)name: P-220, molecular weight: 2000), PCDL (trade(brand)name: ST-602, molecular weight: 2000) molecular weight:.
Isocyano (NCO) content of the isocyanic ester performed polymer of preferred ingredient B is 15-30wt%.
On the other hand, the preparation of B component can be adopted polymerization process well-known to those skilled in the art, such as " plastics industry handbook (urethane): chapter 10 polyurethane elastomer " (Li Junxian chief editor, Chemical Industry Press, the 1st edition, 1999, P406) the related preparation technology of Jie Shaoing.
Specifically, its preparation mainly comprises: earlier polyvalent alcohol is carried out processed, to avoid causing that because of existing of water the side reaction that generates polyureas takes place and then causes the performed polymer quality to descend; Carrying out polyreaction before can be earlier with the MDI preheating, such as being heated to 60 ℃, to avoid causing performed polymer molecular weight distribution ununiformity and quality instability greatly because of temperature variation; Polyreaction is controlled at 50-100 ℃ with temperature of reaction, preferred 60-80 ℃; Reaction times is 1-10 hour, is preferably 3-4 hour; After reaction finishes, can pack.
The use of plastic-blasting polyurethane composition and moulding
Plastic-blasting polyurethane composition of the present invention must make separately packing of component A and B component in accumulating.When being used to make the use of automotive upholstery product, be sprayed into die surface in proportion, form the epidermis of plastic-blasting polyurethane material.Spraying process should be controlled suitable processing condition: such as, regulate material temperature (being called for short the material temperature) and die temperature (being called for short the mould temperature), after spraying one deck water-soluble mold-release agent at die surface then, treating the releasing agent drying, spray lacquer in one deck mould, regulate spraying pressure at last, at mould surface spraying plastic-blasting polyurethane composition of the present invention.In addition, when spray gun moves to definite value, can control the thickness of plastic-blasting polyurethane material by the material flow in the adjusting spraying process.
As plastic-blasting polyurethane material forming mould, its material, size, shape all are not particularly limited, and form the urethane epidermis that meets required specification as long as be beneficial to.Such as, mold material can for: metal, glass, timber, stone material, plastics, rubber, surface are covered with the hard thing of textile materials, or the like.
As plastic-blasting urethane of the present invention, adopt polyureas spraying equipment well-known to those skilled in the art or reaction injection moulding (RIM) high pressure painting equipment, with component A and B component by certain part by weight evenly be sprayed on the die surface in-situ polymerization and form plastic-blasting urethane.
As plastic-blasting urethane of the present invention,, can use the protective layer of lacquer formation plastic-blasting urethane in aliphatic urethane or the esters of acrylic acid mould in order to overcome the xanthochromia defective of aromatic series MDI.According to the color requirement, lacquer can be selected in the mould: BOMEX
8-WIMCK10869 or BOMEX
8-WIMCK10870;
On the other hand, the releasing agent that plastic-blasting urethane of the present invention is adopted can be selected brightening type or sub-smooth type releasing agent as required, such as: BOMEX
TM 07/0066 or BOMEX
TM 07/0205;
Again on the one hand, the processing condition that form plastic-blasting urethane are: the material temperature is at 15-60 ℃; The mould temperature is at 30-90 ℃; The ratio of component A and B component is 100: 30-100: 110 (weight ratios); Spraying pressure: 0.6-25MPa; Demould time is 20-80 second, and injection flow is decided by the thickness requirement of plastic-blasting urethane, such as, when the thickness of plastic-blasting urethane was 1-3mm, flow can be 10-500g/s.
The operating weight ratio of said components A and B component is 100: 30～100: 110, preferred 100: 50～100: 100, and more preferably 100: 52～100: 65.
The above-mentioned releasing agent that is used for plastic-blasting urethane of the present invention is the compound releasing agent of water-soluble organic silicon resin known in the art and wax.
The above-mentioned interior lacquer of mould that is used for plastic-blasting urethane of the present invention is lacquer in aliphatic polyurethane known in the art or the acrylate mould.
The above-mentioned material temperature that is used for plastic-blasting urethane of the present invention is 15-60 ℃, preferred 20-50 ℃, and more preferably 30-45 ℃.
The above-mentioned mould temperature that is used for plastic-blasting urethane of the present invention is 30-90 ℃, preferred 50-80 ℃, and more preferably 60-75 ℃.
Above-mentioned spraying pressure when being used for plastic-blasting polyurethane coating of the present invention is 0.6-25MPa, preferred 8-15MPa, more preferably 9-12MPa.
It is 10-500g/s that the above-mentioned material material that is used for plastic-blasting urethane of the present invention sprays flow velocity, preferred 30-400g/s, more preferably 50-200g/s.
The above-mentioned demould time that is used for plastic-blasting urethane of the present invention is 20-80 second, preferred 30-70s, more preferably 40-60s.
Below in conjunction with embodiment, the present invention is described in further detail.Be noted that the umber of addressing among the following embodiment all is meant weight part.
The plastic-blasting urethane that following each embodiment is obtained carries out the assessment of following technical indicator.
(mechanical property)
Test index comprises: density; Tensile strength; Elongation at break; Thermal ageing back draft intensity (121 ℃, 500h); Elongation at break after the thermal ageing (80 ℃, 168h, 100%RH); Tear strength; Shore A hardness; Winter hardiness.All test, see table 1 for details according to international relevant criterion.
(environmental protection characteristic)
Reference to standard PV3015 and PV3900 according to germany volkswagen standard VW50180 test condensed components and smell respectively.
Measurement result as shown in Table 1 and Table 2.
(flame-retarding characteristic)
Test according to GM9070P.
Embodiment 1
1. the preparation of component A
(1) reactive defoamer (I) is synthetic:
With the catalyzer potassium hydroxide of 100 parts of sorbyl alcohols and 2.3 parts join have stir and the reactor of vacuum system in, be heated to 120 ℃ under stirring, be evacuated to then-0.09MPa, dewatered 120 minutes, logical nitrogen to tensimeter is zero, and then slowly add 1100 parts propylene oxide, keep 100-130 ℃ of temperature of reaction, reaction pressure 0.4MPa, when being reduced to zero, reaction pressure shows then that reaction finishes, obtained the multipolymer of sorbyl alcohol and propylene oxide, through surveying, its hydroxyl value is 176.2mgKOH/g.Cooling, the discharging encapsulation is stand-by.
Join the multipolymer of above-mentioned 100 parts of sorbyl alcohols and propylene oxide and 3.0 parts catalyzer potassium hydroxide in the aforesaid reaction vessel again, be heated to 120 ℃ under stirring, be evacuated to then-0.09MPa, dewatered 120 minutes, logical nitrogen to tensimeter is zero, and then slowly adds 400 parts oxyethane, keep 100-130 ℃ of temperature of reaction, reaction pressure 0.4MPa shows then that when reaction pressure is reduced to zero reaction finishes, and has obtained the multipolymer of sorbyl alcohol and propylene oxide and oxyethane.Through surveying, its hydroxyl value is 33.0mgKOH/g.Be cooled to 90 ℃; add 25 parts distilled water and 15 parts acidic white earth; handled 2 hours down in 90 ℃ under nitrogen protection, be warming up to 120 ℃ of drying and dehydratings under the vacuum tightness of-0.09MPa, it is the reactive defoamer (I) of 80wt% that filtered while hot has obtained ethylene oxide structure unit content.The discharging packing.Press GB 12008.3-89 test, hydroxyl value is 31mgKOH/g.
(2) reactive defoamer (II) is synthetic:
100 parts of sorbyl alcohols; 2.3 parts in catalyzer potassium hydroxide; 900 parts in oxyethane.Operation is with embodiment 1, and having obtained ethylene oxide structure unit content is the reactive defoamer (II) of 100wt%.Press GB 12008.3-89 test, hydroxyl value is 184mgKOH/g.
(3) preparation of component A:
Polyether glycol: GEP-330N is 100 parts;
Chainextender: STEPANPOL
PS-3152 is that 5 parts, DBO are 10 parts;
Non-volatility catalyzer: NIAX
EF-600 is 2.0 parts, Fomrez
UL-1 is 1.0 parts;
Toning mill base: BOMEX
PA-1/0016 is 2 parts;
Reactive defoamer: (I) be 1.0 parts.
Above-mentioned material is joined in the reactor, mix and be heated to 90-110 ℃ to be evacuated to-2 hours package encapsulations of 0.09MPa dehydration get final product.
2. B component is synthetic:
(4) dehydration of polyvalent alcohol: earlier the GEP-330N polyether glycol input with capacity has in the reactor of agitator and vacuum system, is heated to 120 ℃ under stirring, and is evacuated to then-0.09MPa, dewaters 120 minutes, and it is stand-by to be cooled to room temperature then.
(5) preparation of performed polymer: with 100 parts diphenylmethanediisocyanate SUPRASEC
1810 put in another reactor; under nitrogen protection; stirring is warming up to 60 ℃; add (4) set by step then in batches and took off 50 parts of the GEP-330N polyether glycols of water; it is the upper limit that feed rate is no more than 80 ℃ with the reaction mixture heat release, after waiting to add polyvalent alcohol, continues reaction 4 hours; pack after being cooled to room temperature, sealing is deposited.Press GB 12009.4-89 test, NCO content is: 21.2wt%.
3. the preparation of plastic-blasting urethane epidermis:
(6) preparation of plastic-blasting urethane bearing circle epidermis:
With the bearing circle mould (material: stainless steel) be heated to 65 ℃, die surface earlier spray one deck releasing agent, coat with lacquer the general 1-3 of this process minute in spray one deck mould after treating the releasing agent drying; To expect that temperature is adjusted to 33 ℃, spraying pressure is transferred to 10MPa, and the ratio of component A and B component is adjusted to 100: 55, and flow is adjusted to 20g/s, in mould surface spraying 10-15 second, can form the plastic-blasting urethane epidermis of 2mm thickness.By those skilled in the art institute well-known process direct injection elastomer polyurethane, preparing exterior skin is the bearing circle product of plastic-blasting urethane after 30 seconds.
(7) preparation of plastic-blasting urethane dashboard epidermis:
(material: stainless steel) be set in 70 ℃, mass flow is adjusted to 100g/s, sprays 10-15 second, and the demoulding after 30 seconds can form the dashboard plastic-blasting urethane epidermis of 2-3mm thickness, and other processing condition and step are with (6) with the mould temperature of dashboard.
The performance that sprays the plastic-blasting urethane of preparation by above-mentioned processing condition sees Table 1.
Embodiment 2
1. the preparation of component A
Polyether glycol: GEP-330N is that 90 parts, PTMG-1000 are 10 parts;
Chainextender: STEPANPOL
PS-3152 is that 5 parts, DBO are 10 parts;
Non-volatility catalyzer: NIAX
EF-600 is 2.0 parts, Fomrez
UL-1 is 1.0 parts;
Toning mill base: BOMEX
PA-1/0016 is 2 parts;
Reactive defoamer: (II) be 1.0 parts.
Step is with embodiment 1 step (3).
2. B component is synthetic:
Diphenylmethanediisocyanate: SUPRASEC
2020 is 100 parts;
Polyether glycol: GEP-330N is 40 parts;
Step is with embodiment 1 step (4) and (5).Press GB 12009.4-89 test, NCO content is: 19.9%.
3. the preparation of plastic-blasting urethane:
Flow is adjusted to 100g/s, spray 10-15s, the 40s demoulding can form the plastic-blasting urethane epidermis of 2-3mm thickness, and other processing condition and step are with embodiment 1 (6).
The performance that sprays the plastic-blasting urethane of preparation by above-mentioned processing condition sees Table 1.
Embodiment 3
1. the preparation of component A
Polyether glycol: GEP-360N is that 90 parts, P-210 are 10 parts;
Chainextender: STEPANPOL
PS-3152 is that 5 parts, DBO are 10 parts;
Non-volatility catalyzer: NIAX
EF-602 is 2.0 parts, Fomrez
UL-32 is 1.0 parts;
Toning mill base: BOMEX
PA-1/0016 is 2 parts;
Reactive defoamer: (II) be 1.0 parts.
Step is with embodiment 1 step (3).
2. B component is synthetic:
Diphenylmethanediisocyanate: SUPRASEC
1810 is 100 parts;
Polyether glycol: GEP-330N is that 40 parts, PTMG-1000 are 10 parts;
Step is with embodiment 1 step (4) and (5).Press GB 12009.4-89 test, NCO content is: 20.4%.
3. the preparation of plastic-blasting urethane:
Processing condition and step are with embodiment 1 (6).
The performance that sprays the plastic-blasting urethane of preparation by above-mentioned processing condition sees Table 1.
Embodiment 4
1. the preparation of component A
Polyether glycol: GEP-360N is that 90 parts, P-210 are 10 parts;
Chainextender: STEPANPOL
The PS-3152 diglycol phthalate is that 5 parts, DBO are that 9 parts, Ethacure-100 are 1.0 parts;
Non-volatility catalyzer: NIAX
EF-600 is 2.0 parts, Fomrez
UL-32 is 0.6 part;
Toning mill base: BOMEX
PA-1/0016 is 2 parts;
Reactive defoamer: (II) be 1.0 parts.
Step is with embodiment 1 step (3).
2. B component is synthetic:
Diphenylmethanediisocyanate: SUPRASEC
1810 is 100 parts;
Polyether glycol: GEP-330N is 40 parts;
Polyester polyol: P-220 is 10 parts;
Step is with embodiment 1 step (4) and (5).Press GB 12009.4-89 test, NCO content is: 21.9%.
3. the preparation of plastic-blasting urethane:
Processing condition and step are with embodiment 1 (6).
The performance that sprays the plastic-blasting urethane of preparation by above-mentioned processing condition sees Table 1.
Embodiment 5
1. the preparation of component A
Composition is with embodiment 4
Step is with embodiment 1 step (3).
2. B component is synthetic:
Diphenylmethanediisocyanate: SUPRASEC
2020 is 100 parts;
Polyester polyol: P-220 is 10 parts;
Step is with embodiment 1 step (4) and (5).Press GB 12009.4-89 test, NCO content is: 26.0%.
3. the preparation of plastic-blasting urethane:
The ratio of component A and B component is 100: 70, and processing condition and step are with embodiment 1 (6).
The performance that sprays the plastic-blasting urethane of preparation by above-mentioned processing condition sees Table 1.
Embodiment 6
1. the preparation of component A
Composition is with embodiment 4
Step is with embodiment 1 step (3).
2. B component is synthetic:
Diphenylmethanediisocyanate: SUPRASEC
2020 is 40 parts, SUPRASEC
2020 is 60 parts;
Polyester polyol: ST-602 is 5 parts;
Step is with embodiment 1 step (4) and (5).Press GB 12009.4-89 test, NCO content is: 29.2%.
3. the preparation of plastic-blasting urethane:
The ratio of component A and B component is 100: 90, and processing condition and step are with embodiment 1 step (6).
The performance that sprays the plastic-blasting urethane of preparation by above-mentioned processing condition sees Table 1.
The technical feature of table 1. plastic-blasting urethane
As can be seen from Table 1, the tensile strength of various embodiments of the present invention all 〉=more than the 5.0MPa; Elongation at break 〉=290%; Thermal ageing back draft intensity (121 ℃, 500h) 〉=4.5MPa; Elongation at break after the thermal ageing (80 ℃, 168h, 100%RH) 〉=270%; Tear strength 〉=25kN/m; Shore A hardness 〉=65; Winter hardiness is good; Condensed components≤0.3mg; Smell≤2.5.Show that urethane of the present invention has arrived the requirement of automotive upholstery material, therefore have broad application prospects.
Should be understood that plastic-blasting polyurethane composition of the present invention can be applied to various similar leather manufacturing, such as, industries such as upholstery, clothes, shoes and hats.
Though above is example to be used as the automotive upholstery product, technical scheme of the present invention is set forth, but according to of the present invention open, plastic-blasting urethane of the present invention undoubtedly can extend to the application of other near field, such as carrying out surface-treated other materials, anticorrosive, solventless coatings etc. with polyurethane material, this is conspicuous for a person skilled in the art.Therefore, under thought of the present invention, various changes or modification that those skilled in the art can make the present invention on this basis should belong to scope of the present invention equally.
Claims (10)
1. plastic-blasting polyurethane composition, it comprises polyol component A and isocyanic ester performed polymer B component, wherein,
Described component A is a polyol blends, and it is counted by weight and comprises: reactive defoamer of the chainextender of 100 parts polyvalent alcohol, 5-30 part, the non-volatility catalyzer of 1.5-3.5 part, 0.05-5 part and the toning mill base of 0-5 part;
Described B component is the isocyanic ester performed polymer, and the polyvalent alcohol that by diphenylmethanediisocyanate and molecular weight is 1000-8000 is by weight 100: 5-80 carries out polyreaction and gets, and its NCO content is 15-30wt%;
Component A and B component are deposited separately, during use by component A: B component equals 100: 30-100: 110 weight ratio is used,
Wherein, described reactive defoamer is the multipolymer for preparing by the following method: alkali metal hydroxide or bimetal complexes with the 1-50 weight part are catalyzer, at least a low-molecular-weight polyvalent alcohol of 100 weight parts and the propylene oxide and/or the oxyethane of 900-10000 weight part are carried out ring-opening polymerization, then the multipolymer that obtains is made with extra care, filtered, obtain the multipolymer that hydroxyl value is 28-230mgKOH/g.
2. plastic-blasting polyurethane composition according to claim 1 is characterized in that, the hydroxyl value of described reactive defoamer is 28-230mgKOH/g.
3. method for preparing plastic-blasting polyurethane composition as claimed in claim 1 or 2, its following steps:
(1) preparation of component A:
1. preparation feedback defoamer: alkali metal hydroxide or bimetal complexes with the 1-50 weight part are catalyzer, at least a low-molecular-weight polyvalent alcohol of 100 weight parts and the propylene oxide and/or the oxyethane of 900-10000 weight part are carried out ring-opening polymerization, then the multipolymer that obtains is made with extra care, filtered, obtaining hydroxyl value is the reactive defoamer of 28-230mgKOH/g;
2. form polyol blends: at least a polyvalent alcohol of 100 weight parts, at least a chainextender of 5-30 weight part, at least a non-volatility catalyzer of 1.5-3.5 weight part, the above-mentioned reactive defoamer of 0.05-5 weight part and the toning mill base of 0-5 weight part are mixed, thermal dehydration under 80～150 ℃ temperature, get polyol blends, sealing is deposited;
(2) preparation of isocyanic ester performed polymer B component:
One or more diphenylmethanediisocyanates are preheated to 40-60 ℃, by MDI: polyvalent alcohol equals 100: the weight ratio of 5-80, the molecular weight that adds through processed is the polyvalent alcohol of 1000-8000, reacted 1-10 hour down at 50-100 ℃, get the isocyanic ester performed polymer of NCO content 15-30wt%, sealing is deposited.
4. method according to claim 3 is characterized in that, the content of described ethylene oxide structure unit in multipolymer is greater than 50wt%.
5. method according to claim 3 is characterized in that, described alkali metal hydroxide is potassium hydroxide, sodium hydroxide, cesium hydroxide; Bimetal complexes is that six cyanogen close cobalt acid zinc.
6. method according to claim 3 is characterized in that, described low molecular polylol initiator is: a kind of in glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Xylitol, sorbyl alcohol or the sucrose.
7. method according to claim 3 is characterized in that, described reactive defoamer refining comprise distilled water wash, under nitrogen protection with acidic white earth heat treated, dehydration, filtration.
8. method according to claim 3 is characterized in that, the polyvalent alcohol that is used to form isocyanic ester performed polymer B component is a kind of in polyether glycol and the polyester polyol or their mixture.
9. plastic-blasting polyurethane composition according to claim 1 and 2 is used in making automotive upholstery.
10. application according to claim 9, it is characterized in that, described component A and described B component are placed the batch can of spraying equipment respectively, keep the material temperature at 15-60 ℃, by component A: B component is 100: 30-100: 110 weight ratio, described component A and described B component evenly are sprayed on die surface, and 20-80 is after second, from mould, take out, promptly obtain the plastic-blasting urethane of leather character.
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| CN102409553B (en) * | 2011-09-16 | 2013-06-19 | 东台市富安合成材料有限公司 | Method for preparing solvent-free vehicle interior leather based on in-situ polymerization |
| CN103554410A (en) * | 2013-10-19 | 2014-02-05 | 泉州源利鞋材有限公司 | Shoe pad warm in winter and cool in summer as well as preparation method thereof |
| CN103554474B (en) * | 2013-10-31 | 2016-08-17 | 淄博德信联邦化学工业有限公司 | The preparation method of cross-linking agent polyether polyol |
| CN104744683A (en) * | 2013-12-27 | 2015-07-01 | 上海东大化学有限公司 | Xylitol-initiated polyoxyethylene-polyoxypropylene ether copolymer and its preparation method and use |
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| CN109266292A (en) * | 2018-09-06 | 2019-01-25 | 深圳市德顺通科技有限公司 | A kind of environmental protection casting glue |
| CN109553750A (en) * | 2018-12-06 | 2019-04-02 | 上海应用技术大学 | A kind of manufacture craft of high-adhesion polyurethane automobile instrument board |
| CN110696556B (en) * | 2019-09-30 | 2022-03-11 | 浙江华峰新材料有限公司 | Polyurethane tire, composite material for preparing polyurethane tire and preparation method of composite material |
| CN113512174A (en) * | 2021-06-02 | 2021-10-19 | 宁波宝亭生物科技有限公司 | Two-component polyurethane composition and preparation method and application thereof |
| CN115612057B (en) * | 2022-12-16 | 2023-05-09 | 山东一诺威聚氨酯股份有限公司 | Polyurethane elastomer for normal temperature zipper edge sealing coating and preparation method thereof |
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