CN116874966B - Elastomer hose and preparation method thereof - Google Patents
Elastomer hose and preparation method thereof Download PDFInfo
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- CN116874966B CN116874966B CN202310900139.0A CN202310900139A CN116874966B CN 116874966 B CN116874966 B CN 116874966B CN 202310900139 A CN202310900139 A CN 202310900139A CN 116874966 B CN116874966 B CN 116874966B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 50
- 239000000806 elastomer Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 21
- -1 polypropylene carbonate Polymers 0.000 claims abstract description 57
- 229920001470 polyketone Polymers 0.000 claims abstract description 41
- 229920000379 polypropylene carbonate Polymers 0.000 claims abstract description 38
- 239000011258 core-shell material Substances 0.000 claims abstract description 27
- 239000000155 melt Substances 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 150000002978 peroxides Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 97
- 230000003078 antioxidant effect Effects 0.000 claims description 90
- 239000000314 lubricant Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 28
- 239000004698 Polyethylene Substances 0.000 claims description 20
- 229920000573 polyethylene Polymers 0.000 claims description 17
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 16
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 15
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 15
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 15
- 239000008116 calcium stearate Substances 0.000 claims description 15
- 235000013539 calcium stearate Nutrition 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 15
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000077 silane Inorganic materials 0.000 abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 229920002125 Sokalan® Polymers 0.000 description 34
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920006163 vinyl copolymer Polymers 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GQBHYWDCHSZDQU-UHFFFAOYSA-N 4-(2,4,4-trimethylpentan-2-yl)-n-[4-(2,4,4-trimethylpentan-2-yl)phenyl]aniline Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1NC1=CC=C(C(C)(C)CC(C)(C)C)C=C1 GQBHYWDCHSZDQU-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- CFXCGWWYIDZIMU-UHFFFAOYSA-N Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate Chemical compound CCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CFXCGWWYIDZIMU-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an elastomer hose and a preparation method of the elastomer hose, wherein the elastomer hose is prepared by reacting the following raw materials in parts by weight: 100 parts of POE/PAA with a core-shell structure, 1-3 parts of vinyl silane, 10-20 parts of polyketone, 10-20 parts of polypropylene carbonate, 0.1-0.5 part of peroxide initiator and 0.1-0.2 part of catalyst, wherein the core of the POE/PAA with the core-shell structure is POE, the shell is PAA, the number average molecular weight of the polypropylene carbonate is 0.3 ten thousand-3 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 20-30g/10min; when the hose is prepared, the core is POE, the shell is of a core-shell structure POE/PAA of PAA, the PAA shell wraps the POE core, the POE core is protected, meanwhile, polyketone and polypropylene carbonate are added, the hydrolytic property of silane is reduced, and the pressure resistance of the hose is improved.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an elastomer hose and a preparation method of the elastomer hose.
Background
With the development of society and the progress of scientific technology, hoses made of high polymer materials are widely used in various fields such as automobiles, home appliances, gas and liquid transportation systems, and the like. In the current market, hoses are available in a wide variety of forms, such as PVC, PE, EPDM. Among these hoses, PVC generally has a large odor and is liable to generate harmful gases, while PE and EPDM have poor heat resistance, poor weather resistance, and the like.
In order to solve the technical problems of the hoses such as PVC, PE, EPDM and the like, people begin to adopt the elastomer to prepare the hose slowly, and the POE is used for preparing the hose, so that the heat resistance, corrosion resistance and stress cracking resistance of the hose can be greatly improved, and the prepared hose can be widely applied to chemical fluid transportation and building cold and hot water systems. However, when the POE is used for preparing the hose, a peroxide initiator, silane and a catalyst are usually required to be added into the POE, the POE is easy to generate free radicals under the action of the peroxide initiator, and in the hose preparation process, the POE is easy to generate C-C coupling side reaction, so that the quality of the hose is uneven, and the pressure resistance of the hose is reduced; in addition, silane is easy to hydrolyze in the long-term use process, so that the quality of the hose is reduced, and the pressure resistance of the hose is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses an elastomer hose, wherein the core is POE, the shell is a core-shell structure POE/PAA of PAA, the PAA shell wraps the POE core, the POE core is protected, and meanwhile, polyketone and polypropylene carbonate are added, so that the hydrolyzability of silane is reduced, the pressure resistance of the hose is improved, and the stability of the hose is improved.
The invention aims to provide an elastomer hose which is prepared by reacting the following raw materials in parts by weight: 100 parts of POE/PAA with a core-shell structure, 1-3 parts of vinyl silane, 10-20 parts of polyketone, 10-20 parts of polypropylene carbonate, 0.1-0.5 part of peroxide initiator and 0.1-0.2 part of catalyst,
the core of the core-shell structure POE/PAA is POE, the shell is PAA,
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, the melt index at 170 ℃ and 2.16kg is 20-30g/10min,
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is hydrogen, methyl, methoxy, tert-butyl or tert-butoxy, R 2 Is carboxyl or amino; the number average molecular weight is not less than 50000g/mol.
According to the invention, the core is POE, the shell is a core-shell structure POE/PAA of PAA, the PAA shell wraps the POE core, the POE core is protected, the contact between POE and a peroxide initiator is reduced, the side reaction of C-C coupling is not easy to generate in the preparation process of the hose, the pressure resistance of the hose is improved, and the stability of the hose is improved.
The polyketone adopted by the invention contains carboxyl or amino in the molecular structure, on one hand, under the initiation of a peroxide initiator, polyketone and vinyl silane are polymerized to form a copolymer, and hydrogen bond action exists between the polyketone and vinyl copolymer molecules, so that the polyketone and vinyl copolymer are combined more tightly, and further, in the long-term use process, moisture is not easy to contact with silane, and the silane is protected; on the other hand, the polyketone has hydrogen bond action between carboxyl or amino and carboxyl of polyacrylic acid in the molecular structure, so that the tightness degree of the polyketone, vinyl copolymer and core-shell structure POE/PAA is increased, and the contact between POE and peroxide initiator is reduced, so that C-C coupling side reaction is reduced in the hose preparation process, the pressure resistance of the hose is improved, the stability of the hose is improved, and the high temperature resistance of the hose is also improved due to the introduction of polyketone.
The polypropylene carbonate adopted by the invention has a blocking effect, and can block the adhesion of moisture in the hose preparation process, reduce the hydrolyzability of silane, improve the quality of the hose and further improve the pressure resistance of the hose; however, polypropylene carbonate has a problem of poor heat resistance, and the heat resistance of polypropylene carbonate is improved by forming a core-shell structure composite of an ethylene-octene copolymer and polyacrylic acid.
In some embodiments of the invention, the vinylsilane comprises at least one of vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane.
In some preferred embodiments of the present invention, the vinylsilane is selected from vinylmethyldiethoxysilane.
In some embodiments of the invention, the peroxide initiator comprises at least one of dibenzoyl peroxide, dicumyl peroxide, t-butyl peroxypivalate.
In some preferred embodiments of the present invention, the peroxide initiator is selected from dibenzoyl peroxide.
In some embodiments of the invention, the catalyst comprises dibutyltin dilaurate.
In some embodiments of the invention, the elastomer hose further comprises the following raw materials in parts by weight: 0.1 to 0.4 part of antioxidant.
In some preferred embodiments of the present invention, the elastomer hose further comprises the following raw materials in parts by weight: 0.2 parts of antioxidant.
In some embodiments of the invention, the antioxidant is selected from the group consisting of antioxidant 5057, antioxidant TH-1135, antioxidant DLTP, and antioxidant 626 in a mass ratio of 1:2-3:3-5:2-4.
In some preferred embodiments of the invention, the antioxidant is selected from the group consisting of antioxidant 5057, antioxidants TH-1135, antioxidant DLTP and antioxidant 626 in a mass ratio of 1:2:4:3.
In some embodiments of the invention, the elastomer hose further comprises the following raw materials in parts by weight: 0.1 to 0.5 part of lubricant.
In some preferred embodiments of the present invention, the elastomer hose further comprises the following raw materials in parts by weight: 0.3 parts of lubricant.
In some embodiments of the invention, the lubricant is selected from the group consisting of polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:4 to 7:3 to 6.
In some preferred embodiments of the present invention, the lubricant is selected from the group consisting of polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4.
The invention also aims to provide a preparation method of the core-shell POE/PAA, which comprises the following steps:
mixing POE and PAA according to the mass ratio of 3-4:1-2, extruding in a double screw extruder, and granulating.
In some embodiments of the invention, the mass ratio of POE to PAA is 3.5:1.5.
In some embodiments of the invention, the twin screw extruder has a speed of 100 to 140r/min.
In some embodiments of the invention, the barrel temperature of the twin screw extruder is 170 to 210 ℃.
In some embodiments of the invention, the twin screw extruder has a head temperature of 200 to 220 ℃.
Still another object of the present invention is to provide a method for preparing the elastomer hose, comprising the steps of:
s1, adding POE/PAA with a core-shell structure, vinyl silane, polyketone, polypropylene carbonate and a peroxide initiator into a mixer, mixing at 70-90 ℃, and adding a catalyst, an optional antioxidant and an optional lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder to obtain the elastomer hose.
In some embodiments of the invention, in S2, the temperature of the conveying section of the extruder is 90-120 ℃, the temperature of the melt reaction section is 150-190 ℃, the temperature of the die is 160-180 ℃, and the screw aspect ratio is 20-35:1.
In some preferred embodiments of the invention, in S2, the temperature of the conveying section of the extruder is 100 ℃, the temperature of the melt reaction section is 160 ℃, the temperature of the die is 170 ℃, and the screw aspect ratio is 30:1.
Detailed Description
In order to better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the embodiments of the present invention in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Polyketone is prepared by conventional coordination polymerization methods.
POE, i.e. ethylene-octene copolymer, is selected from POE8842.
PAA is polyacrylic acid, the weight average molecular weight is 3000-5000 g/mol, and the PAA is commercially available.
Polypropylene carbonate is commercially available.
The antioxidant 5057 is selected from the group consisting of the basf antioxidant Irganox 5057.
The antioxidants TH-1135 are selected from the Pasteur antioxidant 1135.
The antioxidant DLTP is selected from Basoff antioxidant DLTP.
The antioxidant 626 is selected from the group consisting of basf antioxidants 626.
The polyethylene wax is selected from the group consisting of basf polyethylene wax AF-30.
Example 1: and (3) preparing POE/PAA with a core-shell structure.
Mixing POE and PAA according to the mass ratio of 3.5:1.5, extruding in a double-screw extruder, wherein the rotating speed of the double-screw extruder is 120r/min, the barrel temperature of the double-screw extruder is 190 ℃, the head temperature of the double-screw extruder is 210 ℃, granulating and drying to obtain the POE/PAA with the core-shell structure.
Example 2: preparation of elastomer hoses.
S1, adding 100 parts by mass of POE/PAA with a core-shell structure in example 1, 1 part by mass of vinyl methyl diethoxysilane, 20 parts by mass of polyketone, 10 parts by mass of polypropylene carbonate and 0.5 part by mass of dibenzoyl peroxide into a mixer, mixing at 70-90 ℃, and adding 0.2 part by mass of dibutyltin dilaurate, 0.4 part by mass of antioxidant and 0.5 part by mass of lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder, wherein the temperature of a conveying section of the extruder is 100 ℃, the temperature of a melting reaction section is 160 ℃, the temperature of a die is 170 ℃, and the length-diameter ratio of a screw is 30:1, so as to obtain an elastomer hose;
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 20-30g/10min;
the antioxidant is selected from an antioxidant 5057, an antioxidant TH-1135, an antioxidant DLTP and an antioxidant 626 in a mass ratio of 1:2:4:3;
the lubricant is selected from polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4;
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is hydrogen, R 2 Is carboxyl; the number average molecular weight is 60000-80000 g/mol.
Example 3: preparation of elastomer hoses.
S1, adding 100 parts by mass of POE/PAA with a core-shell structure in example 1, 2 parts by mass of vinyl methyl diethoxysilane, 10 parts by mass of polyketone, 20 parts by mass of polypropylene carbonate and 0.1 part by mass of dibenzoyl peroxide into a mixer, mixing at 70-90 ℃, and adding 0.1 part by mass of dibutyltin dilaurate, 0.1 part by mass of antioxidant and 0.3 part by mass of lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder, wherein the temperature of a conveying section of the extruder is 100 ℃, the temperature of a melting reaction section is 160 ℃, the temperature of a die is 170 ℃, and the length-diameter ratio of a screw is 30:1, so as to obtain an elastomer hose;
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 20-30g/10min;
the antioxidant is selected from an antioxidant 5057, an antioxidant TH-1135, an antioxidant DLTP and an antioxidant 626 in a mass ratio of 1:2:4:3;
the lubricant is selected from polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4;
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is methyl, R 2 Is amino; the number average molecular weight is 65000-90000 g/mol.
Example 4: preparation of elastomer hoses.
S1, adding 100 parts by mass of POE/PAA with a core-shell structure in example 1, 3 parts by mass of vinyl methyl diethoxysilane, 14 parts by mass of polyketone, 15 parts by mass of polypropylene carbonate and 0.2 part by mass of dibenzoyl peroxide into a mixer, mixing at 70-90 ℃, and adding 0.1 part by mass of dibutyltin dilaurate, 0.2 part by mass of antioxidant and 0.1 part by mass of lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder, wherein the temperature of a conveying section of the extruder is 100 ℃, the temperature of a melting reaction section is 160 ℃, the temperature of a die is 170 ℃, and the length-diameter ratio of a screw is 30:1, so as to obtain an elastomer hose;
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 20-30g/10min;
the antioxidant is selected from an antioxidant 5057, an antioxidant TH-1135, an antioxidant DLTP and an antioxidant 626 in a mass ratio of 1:2:4:3;
the lubricant is selected from polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4;
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is methoxy, R 2 Is amino; the number average molecular weight is 60000-75000 g/mol.
Example 5: preparation of elastomer hoses.
S1, adding 100 parts by mass of POE/PAA with a core-shell structure in example 1, 3 parts by mass of vinyl methyl diethoxysilane, 14 parts by mass of polyketone, 15 parts by mass of polypropylene carbonate and 0.2 part by mass of dibenzoyl peroxide into a mixer, mixing at 70-90 ℃, and adding 0.1 part by mass of dibutyltin dilaurate, 0.2 part by mass of antioxidant and 0.1 part by mass of lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder, wherein the temperature of a conveying section of the extruder is 100 ℃, the temperature of a melting reaction section is 160 ℃, the temperature of a die is 170 ℃, and the length-diameter ratio of a screw is 30:1, so as to obtain an elastomer hose;
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 20-30g/10min;
the antioxidant is selected from an antioxidant 5057, an antioxidant TH-1135, an antioxidant DLTP and an antioxidant 626 in a mass ratio of 1:2:4:3;
the lubricant is selected from polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4;
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is tert-butyl, R 2 Is carboxyl; the number average molecular weight is 55000-85000 g/mol.
Example 6: preparation of elastomer hoses.
S1, adding 100 parts by mass of POE/PAA with a core-shell structure in example 1, 3 parts by mass of vinyl methyl diethoxysilane, 14 parts by mass of polyketone, 15 parts by mass of polypropylene carbonate and 0.2 part by mass of dibenzoyl peroxide into a mixer, mixing at 70-90 ℃, and adding 0.1 part by mass of dibutyltin dilaurate, 0.2 part by mass of antioxidant and 0.1 part by mass of lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder, wherein the temperature of a conveying section of the extruder is 100 ℃, the temperature of a melting reaction section is 160 ℃, the temperature of a die is 170 ℃, and the length-diameter ratio of a screw is 30:1, so as to obtain an elastomer hose;
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 20-30g/10min;
the antioxidant is selected from an antioxidant 5057, an antioxidant TH-1135, an antioxidant DLTP and an antioxidant 626 in a mass ratio of 1:2:4:3;
the lubricant is selected from polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4;
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is tert-butoxy, R 2 Is carboxyl; the number average molecular weight is 60000-100000 g/mol.
Comparative example 1: preparation of elastomer hoses.
S1, 50 parts by mass of POE, 50 parts by mass of PAA, 3 parts by mass of vinyl methyl diethoxysilane, 14 parts by mass of polyketone, 15 parts by mass of polypropylene carbonate and 0.2 part by mass of dibenzoyl peroxide are added into a mixer, mixed at 70-90 ℃, and 0.1 part by mass of dibutyltin dilaurate, 0.2 part by mass of antioxidant and 0.1 part by mass of lubricant are added to obtain a mixture;
s2, extruding the mixture through a double-screw extruder, wherein the temperature of a conveying section of the extruder is 100 ℃, the temperature of a melting reaction section is 160 ℃, the temperature of a die is 170 ℃, and the length-diameter ratio of a screw is 30:1, so as to obtain an elastomer hose;
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 20-30g/10min;
the antioxidant is selected from an antioxidant 5057, an antioxidant TH-1135, an antioxidant DLTP and an antioxidant 626 in a mass ratio of 1:2:4:3;
the lubricant is selected from polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4;
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is tert-butyl, R 2 Is carboxyl; the number average molecular weight is 55000-85000 g/mol.
Comparative example 2: preparation of elastomer hoses.
S1, adding 100 parts by mass of POE/PAA with a core-shell structure in example 1, 3 parts by mass of vinyl methyl diethoxysilane, 14 parts by mass of polyketone, 15 parts by mass of polypropylene carbonate and 0.2 part by mass of dibenzoyl peroxide into a mixer, mixing at 70-90 ℃, and adding 0.1 part by mass of dibutyltin dilaurate, 0.2 part by mass of antioxidant and 0.1 part by mass of lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder, wherein the temperature of a conveying section of the extruder is 100 ℃, the temperature of a melting reaction section is 160 ℃, the temperature of a die is 170 ℃, and the length-diameter ratio of a screw is 30:1, so as to obtain an elastomer hose;
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 20-30g/10min;
the antioxidant is selected from an antioxidant 5057, an antioxidant TH-1135, an antioxidant DLTP and an antioxidant 626 in a mass ratio of 1:2:4:3;
the lubricant is selected from polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4;
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is tert-butyl, R 2 Is tert-butyl; the number average molecular weight is 25000-45000 g/mol.
Comparative example 3: preparation of elastomer hoses.
S1, adding 100 parts by mass of POE/PAA with a core-shell structure in example 1, 3 parts by mass of vinyl methyl diethoxysilane, 14 parts by mass of polyketone, 15 parts by mass of polypropylene carbonate and 0.2 part by mass of dibenzoyl peroxide into a mixer, mixing at 70-90 ℃, and adding 0.1 part by mass of dibutyltin dilaurate, 0.2 part by mass of antioxidant and 0.1 part by mass of lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder, wherein the temperature of a conveying section of the extruder is 100 ℃, the temperature of a melting reaction section is 160 ℃, the temperature of a die is 170 ℃, and the length-diameter ratio of a screw is 30:1, so as to obtain an elastomer hose;
the number average molecular weight of the polypropylene carbonate is 4-8 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 5-10g/10min;
the antioxidant is selected from an antioxidant 5057, an antioxidant TH-1135, an antioxidant DLTP and an antioxidant 626 in a mass ratio of 1:2:4:3;
the lubricant is selected from polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4;
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is tert-butyl, R 2 Is carboxyl; number average molecular weight of 55000～85000g/mol。
Comparative example 4: preparation of elastomer hoses.
S1, adding 100 parts by mass of POE/PAA with a core-shell structure in example 1, 3 parts by mass of vinyl methyl diethoxysilane, 14 parts by mass of polyketone, 15 parts by mass of polypropylene carbonate and 0.2 part by mass of dibenzoyl peroxide into a mixer, mixing at 70-90 ℃, and adding 0.1 part by mass of dibutyltin dilaurate, 0.2 part by mass of antioxidant and 0.1 part by mass of lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder, wherein the temperature of a conveying section of the extruder is 100 ℃, the temperature of a melting reaction section is 160 ℃, the temperature of a die is 170 ℃, and the length-diameter ratio of a screw is 30:1, so as to obtain an elastomer hose;
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 20-30g/10min;
the antioxidant is selected from antioxidant 622, antioxidant TH-1135, antioxidant DLTP and antioxidant 626 with the mass ratio of 1:2:4:3;
the lubricant is selected from polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4;
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is tert-butyl, R 2 Is carboxyl; the number average molecular weight is 55000-85000 g/mol.
Comparative example 5: preparation of elastomer hoses.
S1, adding 100 parts by mass of POE/PAA with a core-shell structure in example 1, 3 parts by mass of vinyl methyl diethoxysilane, 14 parts by mass of polyketone, 15 parts by mass of polypropylene carbonate and 0.2 part by mass of dibenzoyl peroxide into a mixer, mixing at 70-90 ℃, and adding 0.1 part by mass of dibutyltin dilaurate, 0.2 part by mass of antioxidant and 0.1 part by mass of lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder, wherein the temperature of a conveying section of the extruder is 100 ℃, the temperature of a melting reaction section is 160 ℃, the temperature of a die is 170 ℃, and the length-diameter ratio of a screw is 30:1, so as to obtain an elastomer hose;
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 20-30g/10min;
the antioxidant is selected from an antioxidant 5057, an antioxidant 1098, an antioxidant DLTP and an antioxidant 626 in a mass ratio of 1:2:4:3;
the lubricant is selected from polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4;
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is tert-butyl, R 2 Is carboxyl; the number average molecular weight is 55000-85000 g/mol.
Comparative example 6: preparation of elastomer hoses.
S1, adding 100 parts by mass of POE/PAA with a core-shell structure in example 1, 3 parts by mass of vinyl methyl diethoxysilane, 14 parts by mass of polyketone, 15 parts by mass of polypropylene carbonate and 0.2 part by mass of dibenzoyl peroxide into a mixer, mixing at 70-90 ℃, and adding 0.1 part by mass of dibutyltin dilaurate, 0.2 part by mass of antioxidant and 0.1 part by mass of lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder, wherein the temperature of a conveying section of the extruder is 100 ℃, the temperature of a melting reaction section is 160 ℃, the temperature of a die is 170 ℃, and the length-diameter ratio of a screw is 30:1, so as to obtain an elastomer hose;
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 20-30g/10min;
the antioxidant is selected from an antioxidant 5057, an antioxidant TH-1135, an antioxidant DSTP and an antioxidant 626 in a mass ratio of 1:2:4:3;
the lubricant is selected from polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4;
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is tert-butyl, R 2 Is carboxyl; the number average molecular weight is 55000-85000 g/mol.
Comparative example 7: preparation of elastomer hoses.
S1, adding 100 parts by mass of POE/PAA with a core-shell structure in example 1, 3 parts by mass of vinyl methyl diethoxysilane, 14 parts by mass of polyketone, 15 parts by mass of polypropylene carbonate and 0.2 part by mass of dibenzoyl peroxide into a mixer, mixing at 70-90 ℃, and adding 0.1 part by mass of dibutyltin dilaurate, 0.2 part by mass of antioxidant and 0.1 part by mass of lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder, wherein the temperature of a conveying section of the extruder is 100 ℃, the temperature of a melting reaction section is 160 ℃, the temperature of a die is 170 ℃, and the length-diameter ratio of a screw is 30:1, so as to obtain an elastomer hose;
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, and the melt index at 170 ℃ and 2.16kg is 20-30g/10min;
the antioxidant is selected from an antioxidant 5057, an antioxidant TH-1135, an antioxidant DLTP and an antioxidant 168 in a mass ratio of 1:2:4:3;
the lubricant is selected from polyethylene wax, ethylene bis-stearamide and calcium stearate in a mass ratio of 1:5:4;
the structural formula of the polyketone is shown as follows:
wherein R is 1 Is tert-butyl, R 2 Is carboxyl; the number average molecular weight is 55000-85000 g/mol.
Performance test:
high temperature resistance test: the test was carried out with reference to GB/T3512-1983.
Pressure resistance: the test was performed with reference to GB/T5563-2006.
The change rate of the breaking strength of the sample = (breaking strength before aging-breaking strength after aging)/breaking strength before aging×100%.
Table 1. Results of the elastomeric hose performance tests of examples 2-6 and comparative examples 1-7.
As can be seen from Table 1, the elastomer hose prepared by the invention has the advantages of high temperature resistance, pressure resistance and the like.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the specific embodiments of the present invention after reading the present specification, and these modifications and variations do not depart from the scope of the invention as claimed in the pending claims.
Claims (10)
1. The elastomer hose is characterized by being prepared by reacting the following raw materials in parts by weight: 100 parts of POE/PAA with a core-shell structure, 1-3 parts of vinyl silane, 10-20 parts of polyketone, 10-20 parts of polypropylene carbonate, 0.1-0.5 part of peroxide initiator and 0.1-0.2 part of catalyst,
the core of the core-shell structure POE/PAA is POE, the shell is PAA,
the number average molecular weight of the polypropylene carbonate is 0.3-3 ten thousand g/mol, the melt index at 170 ℃ and 2.16kg is 20-30g/10min,
the structural formula of the polyketone is shown as follows:
wherein R1 is hydrogen, methyl, methoxy, tert-butyl or tert-butoxy, and R2 is carboxyl or amino; the number average molecular weight is not less than 50000g/mol.
2. The elastomeric hose of claim 1, wherein the vinyl silane comprises at least one of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane, vinyl methyl diethoxy silane.
3. The elastomer hose of claim 1, wherein the peroxide initiator comprises at least one of dibenzoyl peroxide, dicumyl peroxide, and t-butyl peroxypivalate.
4. The elastomeric hose of claim 1, wherein the catalyst comprises dibutyltin dilaurate.
5. The elastomer hose of claim 1, further comprising the following raw materials in parts by weight: 0.1 to 0.4 part of antioxidant.
6. The elastomer hose of claim 5, wherein the antioxidant is selected from the group consisting of antioxidants 5057, antioxidants TH-1135, antioxidants DLTP, and antioxidants 626 in a mass ratio of 1:2-3:3-5:2-4.
7. The elastomer hose of claim 1, further comprising the following raw materials in parts by weight: 0.1 to 0.5 part of lubricant.
8. The elastomer hose of claim 7, wherein the lubricant is selected from the group consisting of polyethylene wax, ethylene bis-stearamide, and calcium stearate in a mass ratio of 1:4 to 7:3 to 6.
9. A method of producing an elastomer hose according to any one of claims 1 to 8, comprising the steps of:
s1, adding POE/PAA with a core-shell structure, vinyl silane, polyketone, polypropylene carbonate and a peroxide initiator into a mixer, mixing at 70-90 ℃, and adding a catalyst, an optional antioxidant and an optional lubricant to obtain a mixture;
s2, extruding the mixture through a double-screw extruder to obtain the elastomer hose.
10. The method of producing an elastomer hose according to claim 9, wherein in S2, the temperature of the conveying section of the extruder is 90 to 120 ℃, the temperature of the melt reaction section is 150 to 190 ℃, the temperature of the die is 160 to 180 ℃, and the screw aspect ratio is 20 to 35:1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104311982A (en) * | 2014-10-15 | 2015-01-28 | 浙江伟星新型建材股份有限公司 | Room-temperature silane self-crosslinking POE hose and preparation method thereof |
| CN104861473A (en) * | 2014-10-11 | 2015-08-26 | 青岛欣展塑胶有限公司 | Core-shell particle toughening PTT polyester and preparation method therefor |
| CN113563593A (en) * | 2021-08-14 | 2021-10-29 | 科艾斯化学有限公司 | Core-shell toughening agent, preparation method thereof and toughened nylon applied by core-shell toughening agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104861473A (en) * | 2014-10-11 | 2015-08-26 | 青岛欣展塑胶有限公司 | Core-shell particle toughening PTT polyester and preparation method therefor |
| CN104311982A (en) * | 2014-10-15 | 2015-01-28 | 浙江伟星新型建材股份有限公司 | Room-temperature silane self-crosslinking POE hose and preparation method thereof |
| CN113563593A (en) * | 2021-08-14 | 2021-10-29 | 科艾斯化学有限公司 | Core-shell toughening agent, preparation method thereof and toughened nylon applied by core-shell toughening agent |
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