CN108250536A - High-ductility anti-crack tube plastics and preparation method thereof - Google Patents
High-ductility anti-crack tube plastics and preparation method thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The present invention relates to plastic-aluminum combined effective plastics, especially a kind of plastic-aluminum combined effective high-ductility cracking resistance plastics and preparation method thereof, the plastics are made of feedstock composition, and on the basis of 100 parts by weight of polyvinyl resin, the feedstock composition includes：100 parts by weight of polyvinyl resin, 20~60 parts by weight of polyether polyol, 10~35 parts by weight of isocyanates, 5~12 parts by weight of inorganic fill particle, 0.5~3 parts by weight of chain extender, 1~10 parts by weight of surfactant；High-ductility anti-crack tube plastics provided by the invention, by introducing polyether polyol on polyvinyl resin surface, and continue to be obtained by the reaction the compound resin of polyvinyl resin and the netted intertexture of polyurethane resin with isocyanates, the compound resin has the advantages that light weight, high intensity and high tenacity, adapt to dilation during thermal shock, for aluminum plastic composite pipe outer layer plastic when can fabulous its service life of raising, the phenomenon that avoiding the occurrence of tube layer separation, cracking.
Description
Technical field
The present invention relates to plastic-aluminum combined effective plastics, especially a kind of plastic-aluminum combined effective high-ductility cracking resistance plastics and its
Preparation method.
Background technology
Aluminum plastic composite pipe is to be followed successively by plastics, hot melt adhesive, aluminium alloy, hot melt adhesive, plastics from inside to outside to form, and is had
Preferable heat-insulating property, inside and outside wall is not perishable, because of inner wall smooth, to fluid resistance very little；Again because with preferable bending
Performance, so installation is more convenient, as water supply line, aluminum plastic composite pipe has enough intensity.
There are mainly three types of the aluminum plastic composite pipe occurred in the market：(1)PE/AL/PE；(2)PE/AL/PEX；(3)PEX/AL/
PEX, wherein, the first be ectonexine all for polyethylene, be for second internal layer for crosslinked polyethylene, outer layer is polyethylene, third
Kind is that ectonexine is all crosslinked polyethylene, and middle part is aluminium layer.The effect of aluminium layer is to increase burst strength, blocking oxygen etc.
So as to which the corrosion to hydraulic pipeline equipment be avoided to threaten, and aluminium layer can improve heat-conducting effect so as to avoid in thermal collecting, resist
Electrostatic and shielding get well and have certain fire retardation；Crosslinked polyethylene compared to conventional polyethylene for, intermolecular knot
Structure is more stable, is more suitable for and building water supply, heating system, still, tubing shrinking percentage made of common crosslinked polyethylene material
Relatively large, user is generally reflected for aluminum plastic composite pipe and steelplastic pipe, copper modeling pipe ectonexine when the contraction of crosslinked polyethylene
Cause circumferential hot melt adhesive that metal is Nian Jie with crosslinked polyethylene securely, the shelf-life of product is shorter, the stabilization of production technology
Property is poor；Also, the aluminum plastic composite pipe as hot-water line in use, due to long-term expanding with heat and contract with cold can cause tube wall dislocation with
Cause in cause leakage the phenomenon that, the service life for directly resulting in product shortens.
Invention content
For the problems of the prior art, the purpose of the present invention is to provide a kind of high-ductility, the tubing plastics of cracking resistance,
The plastics are used in aluminum plastic composite pipe, improve its toughness and the performance of cracking resistance, it is ensured that the aluminum plastic composite pipe of machine-shaping has
Longer service life.
To achieve these goals, the present invention is achieved by the following scheme：A kind of high-ductility anti-crack tube is used
Plastics, the plastics are made of feedstock composition, on the basis of 100 parts by weight of polyvinyl resin, the feedstock composition
Including：100 parts by weight of polyvinyl resin, 20~60 parts by weight of polyether polyol, 10~35 parts by weight of isocyanates, inorganic fill
5~12 parts by weight of particle, 0.5~3 parts by weight of chain extender, 1~10 parts by weight of surfactant.
The present invention introduces polyether polyols alcohol radical by the way that polyvinyl resin is reacted with polyether polyol, in polyethylene surface
Group, and group continuation is made to be reacted with isocyanates, the compound resin that polyvinyl resin interweaves with polyurethane mesh is obtained,
The compound resin has the characteristics that light weight, intensity be high, good toughness, suitable for aluminum plastic composite pipe outer layer plastic when, can not only
Improve integral strength, moreover it is possible to which the phenomenon that adapting to the expansion under thermal shock, preventing cracking improves the use of aluminum plastic composite pipe
Service life.
Further, according to the present invention, on the basis of 100 parts by weight of polyvinyl resin, the feedstock composition includes：
100 parts by weight of polyvinyl resin, 35~50 parts by weight of polyether polyol, 15~30 parts by weight of isocyanates, inorganic fill particle 6
~10 parts by weight, 0.8~2.5 parts by weight of chain extender, 3~8 parts by weight of surfactant.
In the present invention, during compound resin is prepared, inorganic fill particle is added in, can cause inorganic fill particle
It is coated by resin, improves the intensity of the compound resin.The inorganic fill particle is selected from TiO 2 particles, calcium carbonate grain
Son, barium sulfate particles, magnesium sulfate particle, sulfuric acid calcium particle, aluminium oxide particles, magnesia particle, zinc oxide particles, nitridation aluminum shot
One or more kinds of mixtures in son.
Further, it is described under preferable case in order to improve dispersion effect of the inorganic fill particle in compound resin
The grain size of inorganic fill particle is 100~300nm.
Further, it according to the present invention, after polyether polyol introduces, can not only react with polyvinyl resin surface,
Generation polyurethane can also be reacted with isocyanates, it is excellent so as to which the compound resin of polyvinyl resin and polyurethane resin be prepared
In the case of choosing, the polyether polyol is selected from polyether Glycols, polyether-tribasic alcohol, polytetrahydrofuran diol, polypropylene oxide
One kind in glycol.
According to the present invention, the isocyanates can be reacted with polyether polyol produces polyurethane, under preferable case, institute
It states isocyanates and is selected from toluene di-isocyanate(TDI), isophorone diisocyanate, methyl diphenylene diisocyanate, dicyclohexyl
At least one of methane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate.
In the case of, according to the invention it is preferred to, the chain extender in aliphatic diol, aromatic diol at least one
Kind, wherein the aliphatic diol is selected from ethylene glycol, 1,3-BDO, 1,10- certain herbaceous plants with big flowers glycol, Isosorbide-5-Nitrae-cyclohexanediol, 1,8- pungent two
Alcohol, neopentyl glycol, 2- methyl-1,3-propanediols, 2,4- diethyl -1,5- pentanediols and 3- methyl-1s, in 5- pentanediols extremely
Few one kind；Wherein described aromatic diol is selected from hydroquinone double hydroxyethyl ether, resorcinol double hydroxyethyl ether.
According to the present invention, the effect of surfactant is to reduce the surface free energy of inorganic fill particle, improve its
Dispersed homogeneous degree in compound resin, the surfactant is well known to the skilled artisan, specifically, can be with
Enumerate dodecyl alcohol polyoxyethylene ether sodium sulfate, ammonium lauryl sulfate, dodecyl benzene sulfonic acid, sodium secondary alkyl sulfonate, fat
Fat alcohol sodium isethionate, N- lauroyl musculamine acid sodium, coconut acyl methyl taurine sodium, α-sodium olefin sulfonate, dodecyl phosphorus
Ester ester triethanolamine.
The present invention also provides a kind of preparation methods of above-mentioned high-ductility anti-crack tube plastics：
A1：Part polyethylene resin is pre-processed into drying, after being mixed with polyether polyol, isocyanates, 120~150
DEG C by mixer mediate, extruder be granulated be made masterbatch；
A2：Remaining polyvinyl resin is pre-processed into drying, with inorganic fill particle, chain extender, surfactant, step
Masterbatch in A1 is sufficiently mixed in high-speed mixer, then melting mixing, extrusion tie rod, cooling and dicing in blanking to extruder
Obtain plastic pellet.
To prevent polyvinyl resin from degrading in granulation process, in step A1, A2, polyvinyl resin is being granulated
Before need to be dried to moisture content be below 500ppm.
In order to improve dispersion effect of the inorganic fill particle in compound resin, it is preferred that, first will be inorganic in step A2
Particle filled composite adds in surfactant and mixes thoroughly, and after then being mixed with part polyethylene resin, extruded machine, which is granulated to be made in advance, to be contained
There is the master batch of inorganic particle filled composite.By being granulated in advance, the significant dispersion effect for improving inorganic fill particle.
Further, according to the present invention, in the step A2, the extruder is double screw extruder, and screw rod turns
Speed is 230~300r/min, and the temperature of extruder is set in 130~150 DEG C.
Compared with prior art, the present invention has following technique effect：
1st, high-ductility anti-crack tube plastics provided by the invention, by introducing polyether polyols on polyvinyl resin surface
Alcohol, and continue to be obtained by the reaction the compound resin of polyvinyl resin and the netted intertexture of polyurethane resin, the compound tree with isocyanates
Fat has the advantages that light weight, high intensity and high tenacity, adapts to dilation during thermal shock, for the outer of aluminum plastic composite pipe
During layer plastics can fabulous its service life of raising, the phenomenon that avoiding the occurrence of tube layer separation, cracking；
2nd, the preparation method of high-ductility anti-crack tube plastics provided by the invention, it is simple for process, easily operated.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is furture elucidated.
Embodiment 1
A kind of high-ductility anti-crack tube plastics, the plastics are made of feedstock composition, including：
100 parts by weight of polyvinyl resin
42 parts by weight of polyether Glycols
23 parts by weight of toluene di-isocyanate(TDI)
8 parts by weight of TiO 2 particles (average grain diameter 250nm)
1.3 parts by weight of ethylene glycol
5 parts by weight of dodecyl alcohol polyoxyethylene ether sodium sulfate；
The preparation method of above-mentioned high-ductility anti-crack tube plastics is：
A1：By the pretreatment of part polyethylene resin it is dry to moisture content be 500ppm hereinafter, with polyether Glycols, toluene two
It after isocyanates mixing, is mediated at 130 DEG C by mixer, extruder is granulated and masterbatch is made；
A2：By the pretreatment of remaining polyvinyl resin it is dry to moisture content be 500ppm hereinafter, with TiO 2 particles, second
Masterbatch in glycol, dodecyl alcohol polyoxyethylene ether sodium sulfate, step A1 is sufficiently mixed in high-speed mixer, is then passed through
Weightlessness claims melting mixing in blanking to double screw extruder, squeezes out tie rod, obtains plastic pellet by sink water cooling, pelletizing.
Embodiment 2
A kind of high-ductility anti-crack tube plastics, the plastics are made of feedstock composition, including：
100 parts by weight of polyvinyl resin
35 parts by weight of polyether-tribasic alcohol
15 parts by weight of isophorone diisocyanate
6 parts by weight of calcium carbonate particle (average grain diameter 300nm)
0.8 parts by weight of 1,3 butylene glycol
3 parts by weight of ammonium lauryl sulfate；
The preparation method of above-mentioned high-ductility anti-crack tube plastics is：
A1：By the pretreatment of part polyethylene resin it is dry to moisture content be 500ppm hereinafter, with polyether-tribasic alcohol, different Fo Er
It after the mixing of ketone diisocyanate, is mediated at 130 DEG C by mixer, extruder is granulated and masterbatch is made；
A2：By the pretreatment of remaining polyvinyl resin it is dry to moisture content be 500ppm hereinafter, with calcium carbonate particle, 1,3-
Masterbatch in butanediol, ammonium lauryl sulfate, step A1 is sufficiently mixed in high-speed mixer, then claims blanking by weightlessness
Into double screw extruder melting mixing, squeeze out tie rod, plastic pellet obtained by sink water cooling, pelletizing.
Embodiment 3
A kind of high-ductility anti-crack tube plastics, the plastics are made of feedstock composition, including：
100 parts by weight of polyvinyl resin
50 parts by weight of polytetrahydrofuran diol
30 parts by weight of methyl diphenylene diisocyanate
10 parts by weight of barium sulfate particles (average grain diameter 150nm)
2.5 parts by weight of 1,4- cyclohexanediols
8 parts by weight of dodecyl benzene sulfonic acid；
The preparation method of above-mentioned high-ductility anti-crack tube plastics is：
A1：By the pretreatment of part polyethylene resin it is dry to moisture content be 500ppm hereinafter, with polytetrahydrofuran diol, two
It after methylenebis phenyl isocyanate mixing, is mediated at 140 DEG C by mixer, extruder is granulated and masterbatch is made；
A2：By the pretreatment of remaining polyvinyl resin it is dry to moisture content be 500ppm hereinafter, with barium sulfate particles, Isosorbide-5-Nitrae-
Masterbatch in cyclohexanediol, dodecyl benzene sulfonic acid, step A1 is sufficiently mixed in high-speed mixer, under then being claimed by weightlessness
Material to melting mixing in double screw extruder, squeeze out tie rod, plastic pellet obtained by sink water cooling, pelletizing.
Embodiment 4
A kind of high-ductility anti-crack tube plastics, the plastics are made of feedstock composition, including：
100 parts by weight of polyvinyl resin
20 parts by weight of polyoxypropyleneglycol
10 parts by weight of toluene di-isocyanate(TDI)
5 parts by weight of magnesium sulfate particle (average grain diameter 250nm)
0.5 parts by weight of hydroquinone double hydroxyethyl ether
1 parts by weight of sodium secondary alkyl sulfonate；
The preparation method of above-mentioned high-ductility anti-crack tube plastics is：
A1：By the pretreatment of part polyethylene resin it is dry to moisture content be 500ppm hereinafter, with polyoxypropyleneglycol, first
It after phenylene diisocyanate mixing, is mediated at 125 DEG C by mixer, extruder is granulated and masterbatch is made；
A2：By the pretreatment of remaining polyvinyl resin it is dry to moisture content be 500ppm hereinafter, with magnesium sulfate particle, to benzene
Masterbatch in diphenol double hydroxyethyl ether, sodium secondary alkyl sulfonate, step A1 is sufficiently mixed in high-speed mixer, then passes through weightlessness
Claim melting mixing in blanking to double screw extruder, squeeze out tie rod, plastic pellet is obtained by sink water cooling, pelletizing.
Embodiment 5
A kind of high-ductility anti-crack tube plastics, the plastics are made of feedstock composition, including：
100 parts by weight of polyvinyl resin
60 parts by weight of polyether Glycols
35 parts by weight of toluene di-isocyanate(TDI)
12 parts by weight of aluminium oxide particles (average grain diameter 300nm)
3 parts by weight of resorcinol double hydroxyethyl ether
10 parts by weight of fatty alcohol sodium isethionate；
The preparation method of above-mentioned high-ductility anti-crack tube plastics is：
A1：By the pretreatment of part polyethylene resin it is dry to moisture content be 500ppm hereinafter, with polyether Glycols, toluene two
It after isocyanates mixing, is mediated at 120 DEG C by mixer, extruder is granulated and masterbatch is made；
A2：By the pretreatment of remaining polyvinyl resin it is dry to moisture content be 500ppm hereinafter, with aluminium oxide particles, isophthalic
Masterbatch in diphenol double hydroxyethyl ether, fatty alcohol sodium isethionate, step A1 is sufficiently mixed in high-speed mixer, Ran Houtong
Melting mixing in weightless title blanking to double screw extruder is crossed, tie rod is squeezed out, plastic pellet is obtained by sink water cooling, pelletizing.
Embodiment 6
The present embodiment is identical with the high-ductility anti-crack tube plastic formula of embodiment 1, unlike, in preparation method
In, first TiO 2 particles addition surfactant sodium dodecyl base alcohol polyethenoxy ether sodium sulfate is mixed thoroughly, it is then poly- with part
After vinyl mixing, extruded machine is granulated the polyvinyl resin master batch containing TiO 2 particles is made in advance, remaining is constant,
The plastic pellet is prepared.
Comparative example 1
The present embodiment and the high-ductility anti-crack tube plastic formula of embodiment 1 are essentially identical, unlike, wherein being free of
There are TiO 2 particles, remaining is constant, specifically：
The plastics are made of feedstock composition, including：
100 parts by weight of polyvinyl resin
42 parts by weight of polyether Glycols
23 parts by weight of toluene di-isocyanate(TDI)
1.3 parts by weight of ethylene glycol
5 parts by weight of dodecyl alcohol polyoxyethylene ether sodium sulfate；
The preparation method of above-mentioned high-ductility anti-crack tube plastics is：
A1：By the pretreatment of part polyethylene resin it is dry to moisture content be 500ppm hereinafter, with polyether Glycols, toluene two
It after isocyanates mixing, is mediated at 120~150 DEG C by mixer, extruder is granulated and masterbatch is made；
A2：By the pretreatment of remaining polyvinyl resin it is dry to moisture content be 500ppm hereinafter, with ethylene glycol, dodecyl
Masterbatch in alcohol polyethenoxy ether sodium sulfate, step A1 is sufficiently mixed in high-speed mixer, then claims blanking extremely by weightlessness
Melting mixing in double screw extruder squeezes out tie rod, obtains plastic pellet by sink water cooling, pelletizing.
Comparative example 2
The present embodiment and the high-ductility anti-crack tube plastic formula of embodiment 1 are essentially identical, unlike, wherein being free of
There are polyether polyol and isocyanates, remaining is constant, specifically：
The plastics are made of feedstock composition, including：
100 parts by weight of polyvinyl resin
8 parts by weight of TiO 2 particles (average grain diameter 250nm)
1.3 parts by weight of ethylene glycol
5 parts by weight of dodecyl alcohol polyoxyethylene ether sodium sulfate；
The preparation method of above-mentioned high-ductility anti-crack tube plastics is：
By polyvinyl resin pretreatment it is dry to moisture content be 500ppm hereinafter, with TiO 2 particles, ethylene glycol, 12
Alkyl alcohol ethoxylates sodium sulphate is sufficiently mixed in high-speed mixer, then claims blanking to double screw extruder by weightlessness
Middle melting mixing squeezes out tie rod, obtains plastic pellet by sink water cooling, pelletizing.
The plastic pellet obtained in above-described embodiment is extruded into batten,
1st, the impact flexibility of each sample is tested according to the method for GB/T1451-2005,
2nd, according to the elongation at break of the method for GB/T1040.1-2006 test each sample；
3rd, the batten of injection molding is partially placed into high and low temperature alternating humidity test chamber (LRHS-1000B-LJS, Shanghai
Lin Pin instruments limited company) high/low-temperature impact processing is carried out, hot conditions are 60 DEG C, 90%RH, and cryogenic conditions are -30
DEG C, high/low temperature residence time is 1h, recycles 200 times, then tests its impact flexibility retention, is retained with initial impact flexibility
Value ratio is recorded in table 1.
Table 1：
| Impact flexibility/(KJ/m2) | Elongation at break/% | Impact flexibility reservation/% | |
| Embodiment 1 | 42.9 | 6.7 | 32.6 |
| Embodiment 2 | 41.8 | 6.3 | 31.4 |
| Embodiment 3 | 41.6 | 5.9 | 30.8 |
| Embodiment 4 | 40.7 | 5.8 | 30.7 |
| Embodiment 5 | 40.5 | 5.6 | 30.5 |
| Embodiment 6 | 43.4 | 6.9 | 32.8 |
| Comparative example 1 | 39.1 | 5.4 | 29.4 |
| Comparative example 2 | 26.4 | 4.5 | 15.4 |
The tubing plastics provided by the invention it can be seen from above-mentioned test data, in the swell and shrink action of thermal shock
There is down preferable buffering effect.
Basic principle, main feature and the features of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement is both fallen in the range of claimed invention.The scope of protection of present invention is by appended claims
And its equivalent thereof.
Claims (10)
1. a kind of high-ductility anti-crack tube plastics, it is characterised in that：The plastics are made of feedstock composition, with polyethylene
On the basis of 100 parts by weight of resin, the feedstock composition includes：100 parts by weight of polyvinyl resin, polyether polyol 20~60
Parts by weight, 10~35 parts by weight of isocyanates, 5~12 parts by weight of inorganic fill particle, 0.5~3 parts by weight of chain extender, surface are lived
Property 1~10 parts by weight of agent.
2. high-ductility anti-crack tube plastics according to claim 1, wherein, using 100 parts by weight of polyvinyl resin as base
Standard, the feedstock composition include：100 parts by weight of polyvinyl resin, 35~50 parts by weight of polyether polyol, isocyanates 15
~30 parts by weight, 6~10 parts by weight of inorganic fill particle, 0.8~2.5 parts by weight of chain extender, 3~8 parts by weight of surfactant.
3. high-ductility anti-crack tube plastics according to claim 1, wherein, the inorganic fill particle is selected from dioxy
Change titanium particle, calcium carbonate particle, barium sulfate particles, magnesium sulfate particle, sulfuric acid calcium particle, aluminium oxide particles, magnesia particle, oxygen
Change one or more kinds of mixtures in zinc particles, aluminum nitride particle.
4. high-ductility anti-crack tube plastics according to claim 3, wherein, the grain size of inorganic fill particle for 100~
300nm。
5. high-ductility anti-crack tube plastics according to claim 1, wherein, the polyether polyol is selected from polyethers two
One kind in first alcohol, polyether-tribasic alcohol, polytetrahydrofuran diol, polyoxypropyleneglycol.
6. high-ductility anti-crack tube plastics according to claim 1, wherein, the chain extender is selected from aliphatic two
At least one of alcohol, aromatic diol.
7. a kind of preparation method of high-ductility anti-crack tube plastics as described in claim 1~6 any one, feature exist
In：Include the following steps：
A1：Part polyethylene resin is pre-processed into drying, after being mixed with polyether polyol, isocyanates, in 120~150 DEG C of warps
Cross mixer kneading, extruder is granulated and masterbatch is made；
A2：Remaining polyvinyl resin is pre-processed in drying, with inorganic fill particle, chain extender, surfactant, step A1
Masterbatch be sufficiently mixed in high-speed mixer, then melting mixing in blanking to extruder, squeeze out tie rod, cooling and dicing obtains
Plastic pellet.
8. the preparation method of high-ductility anti-crack tube plastics according to claim 7, wherein, step A1, in A2, poly- second
It is below 500ppm that olefine resin, which is dried to moisture content,.
9. the preparation method of high-ductility anti-crack tube plastics according to claim 7, wherein, in step A2, first by nothing
Machine particle filled composite adds in surfactant and mixes thoroughly, and after then being mixed with part polyethylene resin, extruded machine is granulated is made in advance
Master batch containing inorganic fill particle.
10. the preparation method of high-ductility anti-crack tube plastics according to claim 7, wherein, it is described in step A2
Extruder is double screw extruder, and screw speed is 230~300r/min, and the temperature of extruder is set in 130~150 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153944A (en) * | 2011-03-07 | 2011-08-17 | 刘文明 | Solvent-free polyurethane elastomeric coating with self-lubricating effect |
| WO2014189993A1 (en) * | 2013-05-22 | 2014-11-27 | Lubrizol Advanced Materials, Inc. | Articles made from thermoplastic polyurethanes with crystalline chain ends |
| CN105176060A (en) * | 2015-10-26 | 2015-12-23 | 房小明 | Heat-resisting antibacterial thermoplastic polyurethane elastomer and preparation method thereof |
-
2017
- 2017-12-21 CN CN201711396260.5A patent/CN108250536A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153944A (en) * | 2011-03-07 | 2011-08-17 | 刘文明 | Solvent-free polyurethane elastomeric coating with self-lubricating effect |
| WO2014189993A1 (en) * | 2013-05-22 | 2014-11-27 | Lubrizol Advanced Materials, Inc. | Articles made from thermoplastic polyurethanes with crystalline chain ends |
| CN105176060A (en) * | 2015-10-26 | 2015-12-23 | 房小明 | Heat-resisting antibacterial thermoplastic polyurethane elastomer and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 刘青山主编: "《塑料材料》", 31 July 2017, 广东高等教育出版社 * |
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