CN105175678B - A kind of high transparency polyurethane elastomer and preparation method thereof - Google Patents
A kind of high transparency polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN105175678B CN105175678B CN201510565896.2A CN201510565896A CN105175678B CN 105175678 B CN105175678 B CN 105175678B CN 201510565896 A CN201510565896 A CN 201510565896A CN 105175678 B CN105175678 B CN 105175678B
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- 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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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Abstract
The present invention provides a kind of high transparency polyurethane elastomers and preparation method thereof, are mainly prepared by following components：The polypropylene of polyether Glycols mixture, aliphatic isocyanates mixture, chain extender and maleic anhydride grafting；Wherein, polyether Glycols mixture be polytetrahydrofuran ether glycol, polyoxytetramethylene glycol and polycyclic propylene oxide glycol mixture；Aliphatic isocyanates mixture is the mixture of hexamethylene diisocyanate and isophorone diisocyanate；Chain extender is the mixture of Isosorbide-5-Nitrae butanediol and diethylene glycol (DEG).The present invention improves the transparency and Transparent persistence degree of polyurethane elastomer by adjusting the usage ratio of each component using the synergistic effect of HDI and IPDI；Using the mixture of Isosorbide-5-Nitrae butanediol and diethylene glycol (DEG) as chain extender, the hard section of polyurethane elastomer is inhibited to crystallize, be formed simultaneously many away minor segments, increase surface area, the effective deformation for inhibiting soft segment base-material improves mechanical property.
Description
Technical field
The invention belongs to technical field of macromolecules, it is related to a kind of polyurethane elastomer and preparation method thereof more particularly to one
Kind high transparency polyurethane elastomer and preparation method thereof.
Background technology
Polyurethane is a kind of heating soluble high molecular material of fusible and solvent.Its molecule is linear, intermolecular
Seldom crosslinking, glass transition temperature is low, therefore with high intensity, high resiliency and excellent wear-resisting, oil resistant and low temperature tolerance characteristics.
Polyurethane elastomer has two class of polyester-type and polyether-type, white random spherical or cylindrical particle, relative density
1.10~1.25, polyether-type relative density is smaller than polyester-type.The feature that polyurethane elastomer protrudes is excellent in abrasion resistance, resistance to ozone
Property is fabulous, hardness is big, intensity is high, elasticity is good, low temperature resistant, has good oil resistant, chemical-resistant resistance and environmental resistance, in humidity
Polyether polyurethane hydrolytic stability is far more than polyester-type in environment.
Polyurethane elastomer is generally prepared by polyisocyanates, macromolecular polyol and low molecular polylol.Isocyanide
Acid esters forms hard section with low molecular polylol, and macromolecular polyol constitutes soft segment, due to hard section and the soft segment heat with compliance
Incompatible on mechanics results in microphase-separated, and this design feature of polyurethane elastomer imparts its excellent performance,
Relationship between structure and performance is more and more paid close attention to by people.The Microphase Structure and many factors of polyurethane elastomer
(such as macromolecular polyol and chain extender structures) is related, and the variation of these factors can all influence the microfacies of polyurethane elastomer
Structure and mechanical property, thermal stability and optical transparence.
Transparent polyurethane elastomer has excellent optical property, while having the higher machinery of polyurethane elastomer strong again
Degree and very wide hardness range, are suitable for optics and trajectory emits, and can make spectacle lens, bulletproof glass, trade mark nameplate and technique
Product etc..But common polyurethane elastomer is all by aromatic diisocyanate such as Toluene-2,4-diisocyanate, 4- diisocyanate (TDI) or two
Methylenebis phenyl isocyanate (MDI) synthesis, the bridge of two urea of aromatic series is contained with the polyurethane elastomer of these materials synthesis
Key, under ultraviolet light, it is easy to generate the quinoid structure of color development, flavescence can be aoxidized, make the reduction of the product transparency.And it is fatty
(cyclo) aliphatic diisocyanates such as hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) etc., due to being free of benzene
Ring will not occur oxidation and turn yellow, can be used for making the polyurethane products of transparent yellowing-resistant under ultraviolet light.
Patent CN 102040720A disclose a kind of high transparency polyurethane elastomer, are three component system, first, pre-polymerization
Object component：Diisocyanate and polyol reaction obtain the prepolymer of NCO%=6~10%, the preferred TDI- of diisocyanate
80, polyalcohol uses number-average molecular weight in 400~3000 ranges, the polypropylene oxide ethoxylated polyhydric alcohol that degree of functionality is 2；Second is that poly-
Polymer components：Use molecular weight for 1000~5000, polypropylene oxide ethoxylated polyhydric alcohol that degree of functionality is 2 or 3, catalyst and anti-ageing
Agent is made；Third, chain extender component：E-100.Although the high transparency polyurethane elastomer has excellent wearability and impact
Rebound, but its transparency, Transparent persistence degree and high thermal stability are not highly desirable, and it still needs further improvement.
Simultaneously as the optical transparence of polyurethane elastomer can be restricted mutually with barrier property；Using aliphatic isocyanic acid
Ester and polyether polyol reaction can make the reaction force attenuation between macromolecular, hinder molecular crystalline, though polyurethane elastomer can be made
The transparency improve, but its mechanical property can be reduced, therefore the application of polyurethane is made to be limited by very large.
Invention content
Polyurethane elastomer present in for the above-mentioned prior art cannot have both the transparency and good mechanical property, light
It learns the transparency mutually to restrict with barrier property, transparency, the problems such as Transparent persistence degree and high thermal stability is undesirable, it is of the invention
Provide a kind of high transparency polyurethane elastomer.The polyurethane elastomer by adjusting each component usage ratio, and with six
Methylene diisocyanate (HDI) and the mixture of isophorone diisocyanate (IPDI) are mixed as aliphatic isocyanates
Object improves the transparency and Transparent persistence degree of polyurethane elastomer using the synergistic effect of HDI and IPDI；With 1,4-butanediol
With the mixture of diethylene glycol (DEG) as chain extender, symmetrical configuration and the 1,4-butanediol without side group and diethylene glycol (DEG) collective effect, inhibit
The hard section of polyurethane elastomer crystallizes, and is formed simultaneously many away minor segments, increases surface area, the effective change for inhibiting soft segment base-material
Shape improves mechanical property.
For this purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of high transparency polyurethane elastomer, the polyurethane elastomer is by weight
Meter is mainly prepared by following components：
Preferably, the polyurethane elastomer is mainly prepared by following components by weight：
Further preferably, the polyurethane elastomer is mainly prepared by following components by weight：
Wherein, polyether Glycols mixture is polytetrahydrofuran ether glycol, polyoxytetramethylene glycol and polycyclic oxidation third
The mixture of enediol；
Aliphatic isocyanates mixture is the mixture of hexamethylene diisocyanate and isophorone diisocyanate；
Chain extender is the mixture of 1,4-butanediol and diethylene glycol (DEG).
The parts by weight of above-mentioned polyether Glycols mixture can be 50 parts, 53 parts, 55 parts, 57 parts, 60 parts, 63 parts, 65 parts, 67
Part or 70 parts etc.；The parts by weight of aliphatic isocyanates mixture can be 30 parts, 33 parts, 35 parts, 37 parts, 40 parts, 43 parts or 45
Part etc.；The parts by weight of chain extender can be 6 parts, 7 parts, 8 parts, 9 parts or 10 parts etc.；The polyacrylic parts by weight of maleic anhydride grafting can
It is 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 5 parts etc..
Heretofore described " high transparency " refers to the transparent rate of polyurethane elastomer 90% or more.
The present invention uses polyether Glycols mixture for polytetrahydrofuran ether glycol, polyoxytetramethylene glycol and polycyclic oxygen
The mixture for changing propylene glycol, which overcome reduced using material homogeneity caused by single polyether Glycols.
In the present invention, there is IPDI unsymmetric structure, strand to arrange repetitive unit head and the tail isomery, the hard section being made of it
It is not easy to crystallize, but the interaction force of its molecule interchain is weaker, the mechanical properties decrease of polyurethane elastomer can be made；And HDI has
There is symmetrical structure, although there is preferable mechanical property, its symmetrical structure using the polyurethane elastomer that HDI is prepared
Easily crystallization causes the transparency of product to reduce again.The present invention uses the mixture of IPDI and HDI, and chooses suitable chain extender
Overcome the difficulty.The chain extender that the present invention chooses is the mixture of 1,4-butanediol and diethylene glycol (DEG) (DEG), and 1,4-butanediol is
Symmetrical structure and without side group, unsymmetric structure can be generated by being reacted with the IPDI of unsymmetric structure, but when it is reacted with HDI again
Symmetrical structure, which can be generated, influences transparency, therefore the present invention uses the mixing of the mixture of 1,4-butanediol and diethylene glycol (DEG) (DEG),
By adjusting the two ratio, and the dosage of suitable aliphatic isocyanates mixture and chain extender is chosen, it is comprehensive to promote poly- ammonia
The transparency of ester, Transparent persistence degree, and make polyurethane elastomer that there is good mechanical property and high thermal stability simultaneously.
In the present invention, polytetrahydrofuran ether glycol in the polyether Glycols mixture, polyoxytetramethylene glycol and poly-
The mass ratio of epoxidation propylene glycol is (2~3):(2~3):1, such as 2:2:1、2:3:1、3:2:1、2.5:2.5:1、2.3:
2.5:1 or 2.7:3:1 etc., preferably 3:2:1.
In the present invention, two isocyanide of hexamethylene diisocyanate and isophorone in the aliphatic isocyanates mixture
The mass ratio of the mixture of acid esters is 1:(6~10), such as 1:6、1:6.5、1:7、1:8、1:9 or 1:10 etc., preferably 1:(6
~8), further preferably 1:7.If the mass ratio of HDI and IPDI is higher than 1:6, the polyurethane elastomer being prepared can be made
Transparency reduces；If the mass ratio of HDI and IPDI is less than 1:10 can make under the mechanical property for the polyurethane elastomer being prepared
Drop.
Preferably, the mass ratio of 1,4-butanediol and diethylene glycol (DEG) is (3~5) in the chain extender:1, such as 3:1、3.5:
1、4:1、4.5:1 or 5:1 etc., preferably 4:1.The mass ratio of 1,4-butanediol and diethylene glycol (DEG) is in (3~5):1 this range its with
The coefficient effect of HDI and IPDI in aliphatic isocyanates mixture is best.
In the present invention, the polyacrylic preparation method of the maleic anhydride grafting is：By the mixed of polypropylene and maleic anhydride
Object is closed to add twin-screw extrude, after its melting, be added the mixed solution of styrene and the peroxylauric acid tert-butyl ester into
Row melting graft reaction obtains the polypropylene of maleic anhydride grafting.
Both the polypropylene of maleic anhydride grafting and polyurethane elastomers polarity is close, with good compatibility and
Good interfacial adhesion can be formed, to ensure that the physical property of material.
The consumption proportion of material used is by weight in the present invention, in the polyacrylic preparation method of maleic anhydride grafting
Part is calculated as：
Preferably, the consumption proportion of material used is by weight in the polyacrylic preparation method of maleic anhydride grafting
It is calculated as：
Wherein, the parts by weight of maleic anhydride can be 4 parts, 5 parts, 6 parts, 7 parts or 8 parts etc.；The parts by weight of styrene can be 10
Part, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts etc.；The parts by weight of the peroxylauric acid tert-butyl ester can be 0.5 part, 0.6 part, 0.7
Part, 0.8 part, 0.9 part or 1 part etc..
Preferably, the double screw extruder feeding section temperature be 140~160 DEG C, such as 140 DEG C, 142 DEG C, 144 DEG C,
146 DEG C, 148 DEG C, 150 DEG C, 152 DEG C, 154 DEG C, 156 DEG C, 158 DEG C or 160 DEG C etc..
Preferably, the double screw extruder mixing section temperature be 140~160 DEG C, such as 140 DEG C, 142 DEG C, 144 DEG C,
146 DEG C, 148 DEG C, 150 DEG C, 152 DEG C, 154 DEG C, 156 DEG C, 158 DEG C or 160 DEG C etc..
Preferably, the double screw extruder extruding zone temperature be 140~160 DEG C, such as 140 DEG C, 142 DEG C, 144 DEG C,
146 DEG C, 148 DEG C, 150 DEG C, 152 DEG C, 154 DEG C, 156 DEG C, 158 DEG C or 160 DEG C etc..
Preferably, the head temperature of the double screw extruder be 130~140 DEG C, such as 130 DEG C, 132 DEG C, 134 DEG C,
136 DEG C, 138 DEG C or 140 DEG C etc..
Second aspect, the present invention provide above-described method for preparing polyurethane elastic body, and the method includes following
Step：
(1) the polyether Glycols mixture and chain extender of formula ratio are added to the container, 50~60 DEG C under agitation
Dehydration is vacuumized, mixture A is obtained；
(2) it after the aliphatic isocyanates mixture of formula ratio being heated to 70~80 DEG C, is mixed with what is obtained in step (1)
Material A mixing is closed, 1~3h is then stirred at 125~135 DEG C, 10~14h is then cured at 70~80 DEG C, obtains material B；
(3) after mixing by the polypropylene of the maleic anhydride of material B and formula ratio grafting, it is made using double screw extruder
Grain obtains polyurethane elastomer.
Wherein, in step (1) under agitation 50~60 DEG C vacuumize dehydration in temperature can be 50 DEG C, 52 DEG C, 54 DEG C,
56 DEG C, 58 DEG C or 60 DEG C etc.；In step (2) mixture be heated to 70~80 DEG C can be 70 DEG C, 72 DEG C, 74 DEG C, 76 DEG C, 78 DEG C or
80 DEG C etc.；It can be 125 DEG C, 127 DEG C, 130 DEG C, 133 DEG C or 135 DEG C etc. that temperature in 1~3h is stirred at 125~135 DEG C, stirring
Time can be 1h, 1.5h, 2h, 2.5h or 3h etc.；At 70~80 DEG C cure 10~14h in temperature can be 70 DEG C, 72 DEG C, 74
DEG C, 76 DEG C, 78 DEG C or 80 DEG C etc., the curing time can be 10h, 11h, 12h, 13h or 14h etc..
In the present invention, the polyacrylic preparation method of the maleic anhydride grafting is：By the polypropylene of formula ratio and Malaysia
The mixture of acid anhydrides adds twin-screw extrude, and after its melting, styrene and the peroxylauric acid uncle of formula ratio is added
The mixed solution of butyl ester carries out melting graft reaction, obtains the polypropylene of maleic anhydride grafting.
Preferably, the double screw extruder feeding section temperature is 140~160 DEG C.
Preferably, the double screw extruder mixing section temperature is 140~160 DEG C.
Preferably, the double screw extruder extruding zone temperature is 140~160 DEG C.
Preferably, the head temperature of the double screw extruder is 130~140 DEG C.
In the present invention, in step (1) vacuum condition be pressure -0.4~-0.2kPa, such as -0.4kPa, -0.35kPa, -
0.3kPa, -0.25kPa or -0.2kPa etc..
Preferably, in step (1) stir speed (S.S.) be 1000~1200r/min, such as 1000r/min, 1050r/min,
1100r/min, 1150r/min or 1200r/min etc..
Preferably, in step (2) stir speed (S.S.) be 1000~1200r/min, such as 1000r/min, 1050r/min,
1100r/min, 1150r/min or 1200r/min etc..
In the present invention, the feeding section temperature of setting double screw extruder is 130~140 DEG C in the step (3), such as
130 DEG C, 132 DEG C, 134 DEG C, 136 DEG C, 138 DEG C or 140 DEG C etc..
Preferably, the mixing section temperature of setting double screw extruder is 160~170 DEG C in step (3), such as 160 DEG C,
162 DEG C, 164 DEG C, 166 DEG C, 168 DEG C or 170 DEG C etc..
Preferably, the extruding zone temperature of setting double screw extruder is 170~180 DEG C in step (3), such as 170 DEG C,
172 DEG C, 174 DEG C, 176 DEG C, 178 DEG C or 180 etc..
Preferably, the head temperature of setting double screw extruder is 170~180 DEG C in step (3), for example, 170 DEG C, 172
DEG C, 174 DEG C, 176 DEG C, 178 DEG C or 180 etc..
Compared with prior art, the invention has the advantages that：
(1) usage ratio of the invention by adjusting each component, and with hexamethylene diisocyanate (HDI) and different Fo Er
The mixing of ketone diisocyanate (IPDI) is carried as object aliphatic isocyanates mixture using the synergistic effect of HDI and IPDI
The transparency and Transparent persistence degree of high polyurethane elastomer make its light transmittance reach 95% or more, and mist degree is less than 1.6%, certainly
After being placed 180 days under the conditions of so, light transmittance remains to keep previous level.
(2) present invention using the mixture of 1,4-butanediol and diethylene glycol (DEG) as chain extender, symmetrical configuration and without side group 1,
4- butanediols and diethylene glycol (DEG) collective effect inhibit the hard section of polyurethane elastomer to crystallize, and are formed simultaneously many away minor segments, increase table
Area, the effective deformation for inhibiting soft segment base-material, improves mechanical property, so that its tensile strength is reached 80MPa, elongation at break can
Up to 800%, rebound degree reaches 85%.
Specific implementation mode
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
Light transmittance and mist degree test method are as follows in the present invention：
Between uncured PU is poured into two layers of polycarbonate transparent substrate (2mm is thick), cure 4h at 120 DEG C.It places
The PC/PU/PC composite boards cut out (50mm × 12mm × 7mm) are tested on 721B type spectrophotometers after 10 days.
The mechanical property of each embodiment of the present invention is tested by GB/T 1040-1979.
Embodiment 1：
(1) polypropylene of maleic anhydride grafting is prepared：
Agent adds twin-screw extrude the mixture of 100 parts of polypropylene and 6 parts of maleic anhydrides by weight, and setting is double
Screw extruder feeding section temperature, mixing section temperature, extruding zone temperature and head temperature be respectively 150 DEG C, 150 DEG C, 150 DEG C and
135 DEG C, after its melting, the mixed solution of 13 parts of styrene of addition and 0.7 part of peroxylauric acid tert-butyl ester carries out melting and connects
Branch reaction, obtains the polypropylene of maleic anhydride grafting.
(2) polyurethane elastomer is prepared：
By 58 parts of polyether Glycols mixtures (wherein, polytetrahydrofuran ether glycol, polyoxytetramethylene glycol and polycyclic oxygen
The mass ratio for changing propylene glycol is 3:2:And 7.5 parts of chain extender (wherein, mass ratioes 4 of 1,4-butanediol and diethylene glycol (DEG) 1):1) add
Enter in container, vacuumizes -0.3kPa dehydrations for 55 DEG C under 1050r/min stir speed (S.S.)s, obtain mixture A；
By 37 parts of aliphatic isocyanates mixtures (wherein, hexamethylene diisocyanate and isophorone diisocyanates
The mass ratio of the mixture of ester is 1:7) it after being heated to 75 DEG C, is mixed with the mixture A obtained in step (1), then in 130 DEG C
Under 2h stirred with the rate of 1100r/min, then cure 12h at 75 DEG C, obtain material B；
The polypropylene that material B and 3.5 parts of maleic anhydrides are grafted after mixing, is granulated to obtain using double screw extruder
Polyurethane elastomer, wherein be respectively set the setting feeding section temperature of double screw extruder, mixing section temperature, extruding zone temperature and
Head temperature is 135 DEG C, 165 DEG C, 175 DEG C and 175 DEG C.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Embodiment 2：
(1) polypropylene of maleic anhydride grafting is prepared：
Agent adds twin-screw extrude the mixture of 100 parts of polypropylene and 8 parts of maleic anhydrides by weight, and setting is double
Screw extruder feeding section temperature, mixing section temperature, extruding zone temperature and head temperature be respectively 140 DEG C, 140 DEG C, 140 DEG C and
130 DEG C, after its melting, the mixed solution that 15 parts of styrene and 1 part of peroxylauric acid tert-butyl ester are added carries out fusion-grafting
Reaction obtains the polypropylene of maleic anhydride grafting.
(2) polyurethane elastomer is prepared：
By 55 parts of polyether Glycols mixtures (wherein, polytetrahydrofuran ether glycol, polyoxytetramethylene glycol and polycyclic oxygen
The mass ratio for changing propylene glycol is 2.5:2.5:And 7 parts of chain extender (wherein, mass ratioes 5 of 1,4-butanediol and diethylene glycol (DEG) 1):1)
It is added to the container, vacuumizes -0.4kPa dehydrations for 50 DEG C under 1000r/min stir speed (S.S.)s, obtain mixture A；
By 35 parts of aliphatic isocyanates mixtures (wherein, hexamethylene diisocyanate and isophorone diisocyanates
The mass ratio of the mixture of ester is 1:8) it after being heated to 70 DEG C, is mixed with the mixture A obtained in step (1), then in 125 DEG C
Under 3h stirred with the rate of 1000r/min, then cure 14h at 70 DEG C, obtain material B；
The polypropylene that material B and 3 parts of maleic anhydrides are grafted after mixing, is granulated using double screw extruder and is gathered
Urethane elastomer, wherein feeding section temperature, mixing section temperature, extruding zone temperature and the machine of setting double screw extruder is respectively set
Head temperature is 130 DEG C, 160 DEG C, 170 DEG C and 170 DEG C.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Embodiment 3：
(1) polypropylene of maleic anhydride grafting is prepared：
Agent adds twin-screw extrude the mixture of 100 parts of polypropylene and 4 parts of maleic anhydrides by weight, and setting is double
Screw extruder feeding section temperature, mixing section temperature, extruding zone temperature and head temperature be respectively 160 DEG C, 160 DEG C, 160 DEG C and
140 DEG C, after its melting, the mixed solution of 10 parts of styrene of addition and 0.5 part of peroxylauric acid tert-butyl ester carries out melting and connects
Branch reaction, obtains the polypropylene of maleic anhydride grafting.
(2) polyurethane elastomer is prepared：
By 65 parts of polyether Glycols mixtures (wherein, polytetrahydrofuran ether glycol, polyoxytetramethylene glycol and polycyclic oxygen
The mass ratio for changing propylene glycol is 2:2:And 8 parts of chain extender (wherein, mass ratioes 3 of 1,4-butanediol and diethylene glycol (DEG) 1):1) it is added
In container, vacuumizes -0.2kPa dehydrations for 60 DEG C under 1200r/min stir speed (S.S.)s, obtain mixture A；
By 40 parts of aliphatic isocyanates mixtures (wherein, hexamethylene diisocyanate and isophorone diisocyanates
The mass ratio of the mixture of ester is 1:6) it after being heated to 80 DEG C, is mixed with the mixture A obtained in step (1), then in 135 DEG C
Under 1h stirred with the rate of 1200r/min, then cure 10h at 80 DEG C, obtain material B；
The polypropylene that material B and 4 parts of maleic anhydrides are grafted after mixing, is granulated using double screw extruder and is gathered
Urethane elastomer, wherein feeding section temperature, mixing section temperature, extruding zone temperature and the machine of setting double screw extruder is respectively set
Head temperature is 140 DEG C, 170 DEG C, 180 DEG C and 180 DEG C.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Embodiment 4：
Except the dosage of polyether Glycols mixture in step (2) is 70 parts of (wherein, polytetrahydrofuran ether glycol, polyoxies four
The mass ratio of methylene glycol and polycyclic propylene oxide glycol is 3:3:1), chain extender dosage is 10 parts, aliphatic isocyanates
Amount of mixture is 45 parts of (wherein, mass ratioes of hexamethylene diisocyanate and the mixture of isophorone diisocyanate
It is 1:10) and the polyacrylic dosage of maleic anhydride grafting is 5 especially that other steps are in the same manner as in Example 1.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Embodiment 5：
Except the dosage of polyether Glycols mixture in step (2) is 50 parts, chain extender dosage is 6 parts, aliphatic isocyanic acid
Ester admixture dosage be 30 parts and the polyacrylic dosage of maleic anhydride grafting be 2 especially, other steps in embodiment 1
It is identical.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 1：
Other than aliphatic isocyanates mixture is all substituted for isophorone diisocyanate in preparation process, other
Step is in the same manner as in Example 1.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 2：
Other than aliphatic isocyanates mixture is all substituted for hexamethylene diisocyanate in preparation process, other
Step is in the same manner as in Example 1.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 3：
Other than chain extender uses 1,4-butanediol in preparation process, other steps are in the same manner as in Example 1.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 4：
Other than chain extender uses diethylene glycol (DEG) in preparation process, other steps are in the same manner as in Example 1.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 5：
Other than chain extender uses 1,3-BDO in preparation process, other steps are in the same manner as in Example 1.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 6：
In addition to hexamethylene diisocyanate and isophorone two are different in aliphatic isocyanates mixture in preparation process
The mass ratio of the mixture of cyanate is 1:Outside 2, other steps are in the same manner as in Example 1.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 7：
In addition to hexamethylene diisocyanate and isophorone two are different in aliphatic isocyanates mixture in preparation process
The mass ratio of the mixture of cyanate is 1:Outside 15, other steps are in the same manner as in Example 1.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 8：
Other than not adding the polypropylene of maleic anhydride grafting in preparation process, other steps are in the same manner as in Example 1.
Polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Table 1：Embodiment 1-5 and comparative example 1-8 polyurethane elastomers are tested for the property table
The result of integrated embodiment 1-5 and comparative example 1-8 can be seen that the present invention by adjusting the amount ratio of each component
Example, and it is different using the mixing of hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) as object aliphatic
Cyanate ester compositions improve the transparency and Transparent persistence degree of polyurethane elastomer, make using the synergistic effect of HDI and IPDI
Its light transmittance reaches 95% or more, and mist degree is less than 1.6%, and after placing 180 days under field conditions (factors), light transmittance remains to keep former
There is level.Meanwhile the present invention is using the mixture of 1,4-butanediol and diethylene glycol (DEG) as chain extender, symmetrical configuration and without side group 1,
4- butanediols and diethylene glycol (DEG) collective effect inhibit the hard section of polyurethane elastomer to crystallize, and are formed simultaneously many away minor segments, increase table
Area, the effective deformation for inhibiting soft segment base-material, improves mechanical property, so that its tensile strength is reached 80MPa, elongation at break can
Up to 800%, rebound degree reaches 85%.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (28)
1. a kind of high transparency polyurethane elastomer, which is characterized in that the polyurethane elastomer is by weight mainly by following
Component is prepared：
Wherein, polyether Glycols mixture is polytetrahydrofuran ether glycol, polyoxytetramethylene glycol and polyoxypropyleneglycol
Mixture；
Aliphatic isocyanates mixture is the mixture of hexamethylene diisocyanate and isophorone diisocyanate；
Chain extender is the mixture of 1,4-butanediol and diethylene glycol (DEG)；
The mixture of hexamethylene diisocyanate and isophorone diisocyanate in the aliphatic isocyanates mixture
Mass ratio be 1:(6~10)；
The mass ratio of 1,4-butanediol and diethylene glycol (DEG) is (3~5) in the chain extender:1.
2. polyurethane elastomer according to claim 1, which is characterized in that the polyurethane elastomer is main by weight
It to be prepared by following components：
3. polyurethane elastomer according to claim 1, which is characterized in that the polyurethane elastomer is main by weight
It to be prepared by following components：
4. polyurethane elastomer according to claim 1, which is characterized in that poly- tetrahydrochysene in the polyether Glycols mixture
The mass ratio of furans ether glycol, polyoxytetramethylene glycol and polyoxypropyleneglycol is (2~3):(2~3):1.
5. polyurethane elastomer according to claim 4, which is characterized in that poly- tetrahydrochysene in the polyether Glycols mixture
The mass ratio of furans ether glycol, polyoxytetramethylene glycol and polyoxypropyleneglycol is 3:2:1.
6. polyurethane elastomer according to claim 1, which is characterized in that six in the aliphatic isocyanates mixture
The mass ratio of methylene diisocyanate and the mixture of isophorone diisocyanate is 1:(6~8).
7. polyurethane elastomer according to claim 6, which is characterized in that six in the aliphatic isocyanates mixture
The mass ratio of methylene diisocyanate and the mixture of isophorone diisocyanate is 1:7.
8. polyurethane elastomer according to claim 1, which is characterized in that 1,4-butanediol and two sweet in the chain extender
The mass ratio of alcohol is 4:1.
9. polyurethane elastomer according to claim 1, which is characterized in that the polyacrylic system of the maleic anhydride grafting
Preparation Method is：The mixture of polypropylene and maleic anhydride is added twin-screw extrude, after its melting after, be added styrene and
The mixed solution of the peroxylauric acid tert-butyl ester carries out melting graft reaction, obtains the polypropylene of maleic anhydride grafting.
10. polyurethane elastomer according to claim 9, which is characterized in that the maleic anhydride is grafted polyacrylic
The consumption proportion of material used is calculated as by weight in preparation method：
11. polyurethane elastomer according to claim 10, which is characterized in that the maleic anhydride is grafted polyacrylic
The consumption proportion of material used is calculated as by weight in preparation method：
12. polyurethane elastomer according to claim 9, which is characterized in that the double screw extruder feeding section temperature
It is 140~160 DEG C.
13. polyurethane elastomer according to claim 9, which is characterized in that the double screw extruder mixing section temperature
It is 140~160 DEG C.
14. polyurethane elastomer according to claim 9, which is characterized in that the double screw extruder extruding zone temperature
It is 140~160 DEG C.
15. polyurethane elastomer according to claim 9, which is characterized in that the head temperature of the double screw extruder
It is 130~140 DEG C.
16. according to claim 1-15 any one of them method for preparing polyurethane elastic body, which is characterized in that the method
Include the following steps：
(1) the polyether Glycols mixture and chain extender of formula ratio are added to the container, are taken out very for 50~60 DEG C under agitation
Sky dehydration, obtains mixture A；
(2) after the aliphatic isocyanates mixture of formula ratio being heated to 70~80 DEG C, with the mixture obtained in step (1)
A is mixed, and 1~3h is then stirred at 125~135 DEG C, and 10~14h is then cured at 70~80 DEG C, obtains material B；
(3) after mixing by the polypropylene of the maleic anhydride of material B and formula ratio grafting, it is granulated using double screw extruder
To polyurethane elastomer.
17. preparation method according to claim 16, which is characterized in that the polyacrylic preparation of the maleic anhydride grafting
Method is：The mixture of the polypropylene of formula ratio and maleic anhydride is added twin-screw extrude, after its melting, addition is matched
The mixed solution of the styrene and the peroxylauric acid tert-butyl ester just measured carries out melting graft reaction, obtains maleic anhydride grafting
Polypropylene.
18. preparation method according to claim 17, which is characterized in that the double screw extruder feeding section temperature is
140~160 DEG C.
19. preparation method according to claim 17, which is characterized in that the double screw extruder mixing section temperature is
140~160 DEG C.
20. preparation method according to claim 17, which is characterized in that the double screw extruder extruding zone temperature is
140~160 DEG C.
21. preparation method according to claim 17, which is characterized in that the head temperature of the double screw extruder is
130~140 DEG C.
22. preparation method according to claim 16, which is characterized in that in step (1) vacuum condition be pressure -0.4~-
0.2kPa。
23. preparation method according to claim 16, which is characterized in that in step (1) stir speed (S.S.) be 1000~
1200r/min。
24. preparation method according to claim 16, which is characterized in that in step (2) stir speed (S.S.) be 1000~
1200r/min。
25. preparation method according to claim 16, which is characterized in that double screw extruder is arranged in the step (3)
Feeding section temperature be 130~140 DEG C.
26. preparation method according to claim 16, which is characterized in that setting double screw extruder is mixed in step (3)
It is 160~170 DEG C to close section temperature.
27. preparation method according to claim 16, which is characterized in that setting double screw extruder squeezes in step (3)
It is 170~180 DEG C to go out section temperature.
28. preparation method according to claim 16, which is characterized in that the machine of setting double screw extruder in step (3)
Head temperature is 170~180 DEG C.
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| MY169084A (en) * | 2011-12-20 | 2019-02-14 | Cytec Engineered Mat Inc | Dry fibrous material for subsequent resin infusion |
| CN105860508A (en) * | 2016-06-08 | 2016-08-17 | 东莞市吉鑫高分子科技有限公司 | Rolling-grade thermoplastic polyurethane elastomer and preparing method thereof |
| CN106084746A (en) * | 2016-06-08 | 2016-11-09 | 苏州市雄林新材料科技有限公司 | A kind of transparent high abrasion TPU film and preparation method thereof |
| CN106243318B (en) * | 2016-07-28 | 2018-12-04 | 东莞市吉鑫高分子科技有限公司 | A kind of mixing calendering type thermoplastic polyurethane elastomer and preparation method thereof |
| CN107141441A (en) * | 2017-06-02 | 2017-09-08 | 东莞市吉鑫高分子科技有限公司 | A kind of low-refraction high transparency TPUE and preparation method thereof |
| CN107383328B (en) * | 2017-06-27 | 2021-01-05 | 烟台观复光电材料有限公司 | Flexible bendable polyurethane optical material with barrier protection function, preparation method thereof, transparent flexible optical component and application thereof |
| CN107383325B (en) * | 2017-06-28 | 2020-02-07 | 苏州奥斯汀新材料科技有限公司 | Preparation method of high-transparency thermoplastic polyurethane elastomer |
| CN109651579A (en) * | 2018-12-04 | 2019-04-19 | 中山市志捷鞋业技术服务有限公司 | A kind of manufacturing process of Transparent PU-Soles |
| CN109735240A (en) * | 2019-01-04 | 2019-05-10 | 深圳市高仁电子新材料有限公司 | Thermoplastic polyurethane optical adhesive film and its applying method |
| CN110982251A (en) * | 2019-11-08 | 2020-04-10 | 安徽潜隆机电科技有限公司 | Gas mask elastic lens and preparation method thereof |
| CN112812728B (en) * | 2021-02-05 | 2023-03-17 | 乐凯胶片股份有限公司 | Polyurethane adhesive and preparation method and application thereof |
| CN112920367B (en) * | 2021-02-27 | 2022-04-19 | 福州大学 | High-transparency easy-to-machine-formed BI-SiO2Preparation method of TPU |
| CN113072805A (en) * | 2021-03-16 | 2021-07-06 | 浙江洛克新材料股份有限公司 | TPU film for protective clothing |
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