CN102977441B - Radiation crosslinking chloroprene rubber heat shrinkage material and preparation method thereof - Google Patents
Radiation crosslinking chloroprene rubber heat shrinkage material and preparation method thereof Download PDFInfo
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- CN102977441B CN102977441B CN201210533937.6A CN201210533937A CN102977441B CN 102977441 B CN102977441 B CN 102977441B CN 201210533937 A CN201210533937 A CN 201210533937A CN 102977441 B CN102977441 B CN 102977441B
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Abstract
The invention discloses a radiation crosslinking chloroprene rubber heat shrinkage material which comprises the following components in parts by weight: 100 parts of polyolefin base material; 5-20 parts of chloroprene rubber; 5-20 parts of chlorinated polyethylene; 0.5-3 parts of antioxygen; 1-15 parts of plasticizer and 1-5 parts of color master batch. The radiation crosslinking chloroprene rubber heat shrinkage material has the advantages of low temperature resistance, oil resistance and thermal aging resistance.
Description
Technical field
The present invention relates to a kind of heat-shrinkage material and preparation method thereof.
Background technology
The range of application of heat-shrinkage material widely, comprises the insulation protection etc. of the cables such as automobile, electronics, building, military project.But, oil resistant, heat-proof aging low at temperature requirement require high occasion, general polyolefins material contracting with heat can not meet requirement, and result of use is poor.
Summary of the invention
The technical problem to be solved in the present invention is: the problem overcoming existing polyolefins heat-shrinkage material resistance to low temperature, oil resistance, heat aging property difference, provides a kind of low temperature resistant, radiation crosslinking chloroprene rubber heat-shrinkage material that oil resistance, heat aging property are good and preparation method thereof.
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: a kind of radiation crosslinking chloroprene rubber heat-shrinkage material, and it is made up of the following component with weight parts:
Polyolefin substrate 100 parts;
Chloroprene rubber 5-20 part;
Chlorinatedpolyethylene 5-20 part;
Oxidation inhibitor 0.5-3 part;
Softening agent 1-15 part;
Masterbatch 1-5 part.
The further restriction of technique scheme is: described polyolefin substrate is one or more the mixture in following material: polyethylene; Ethylene-vinyl acetate copolymer; Ethylene butyl acrylate; Ethylene methacrylic acid copolymer.
The further restriction of technique scheme is: described chloroprene rubber is the slow non-sulphur adjustment type chloroprene rubber of crystallization velocity, and mooney viscosity is 48 ± 5.
The further restriction of technique scheme is: described oxidation inhibitor is the composite of a kind of in phenolic antioxidant, both ester kind antioxidants or two kinds, and the composite mass ratio of this phenolic antioxidant, ester kind antioxidant is (0.5-3): (0.5-3);
Described phenolic antioxidant is one or more composite in following material: 2,4,6-tri-butyl-phenol; Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Described ester kind antioxidant is one or more composite in following material: β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid; Tyox B; Three [2.4-di-tert-butyl-phenyl] phosphorous acid ester; Triphenyl phosphite.
The further restriction of technique scheme is: described softening agent is ester plasticizer, is one or more composite in following material: dioctyl phthalate (DOP), dibutyl phthalate, dioctyl sebacate;
The composite mass ratio of above-mentioned dioctyl phthalate (DOP), dibutyl phthalate, dioctyl sebacate three is (1-15): (1-15): (1-15).
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: the preparation method of described radiation crosslinking chloroprene rubber heat-shrinkage material, comprises the following steps:
Step 1: take polyolefin substrate 100 parts, chloroprene rubber 5-20 part, chlorinatedpolyethylene 5-20 part, oxidation inhibitor 0.5-3 part, softening agent 1-15 part, Masterbatch 1-5 part according to parts by weight, at room temperature fully mix;
Step 2: the broken rear twin screw extruder of material cooling step 1 mixed extrudes tie rod, water-cooled in 130 DEG C of-180 DEG C of temperature ranges, air-dry, pelletizing;
Step 3: above-mentioned material grain is extruded into tubulose at 130 DEG C of-180 DEG C of temperature;
Step 4: by aforementioned tubes through gamma-rays or rumbatron radiation, radiation dose 80-200KGY;
Step 5: then at 100-200 DEG C of temperature, aforementioned tubes expansion is stretched to 0.5-3 doubly heat-shrink tube.
The further restriction of technique scheme is: described polyolefin substrate is one or more the mixture in following material: polyethylene; Ethylene-vinyl acetate copolymer; Ethylene butyl acrylate; Ethylene methacrylic acid copolymer.
The further restriction of technique scheme is: described chloroprene rubber is the slow non-sulphur adjustment type chloroprene rubber of crystallization velocity, and mooney viscosity is 48 ± 5.
The further restriction of technique scheme is: described oxidation inhibitor is the composite of a kind of in phenolic antioxidant, both ester kind antioxidants or two kinds, and the composite mass ratio of this phenolic antioxidant, ester kind antioxidant is (0.5-3): (0.5-3);
Described phenolic antioxidant is one or more composite in following material: 2,4,6-tri-butyl-phenol; Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Described ester kind antioxidant is one or more composite in following material: β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid; Tyox B; Three [2.4-di-tert-butyl-phenyl] phosphorous acid ester; Triphenyl phosphite.
The further restriction of technique scheme is: described softening agent is ester plasticizer, is one or more composite in following material: dioctyl phthalate (DOP), dibutyl phthalate, dioctyl sebacate;
The composite mass ratio of above-mentioned dioctyl phthalate (DOP), dibutyl phthalate, dioctyl sebacate three is (1-15): (1-15): (1-15).
Compared with prior art, the present invention has following beneficial effect: cross-linking radiation chloroprene rubber heat-shrinkage material of the present invention can be used for making various thermal contraction device, comprises heat-shrink tube, can be low temperature resistant-70 DEG C, and oil resistant, heat aging property are good.The present invention expands kind and the range of application of thermal contraction product, has also opened up the new application space of chloroprene rubber simultaneously.Aforementioned tubes performance is good, and preparation method is simple, is suitable for suitability for industrialized production.
Embodiment
The present invention proposes a kind of radiation crosslinking chloroprene rubber heat-shrinkage material, and it is made up of the following component with weight parts:
Polyolefin substrate 100 parts;
Chloroprene rubber 5-20 part;
Chlorinatedpolyethylene 5-20 part;
Oxidation inhibitor 0.5-3 part;
Softening agent 1-15 part;
Masterbatch 1-5 part.
Described polyolefin substrate is one or more the mixture in following material: polyethylene; Ethylene-vinyl acetate copolymer; Ethylene butyl acrylate; Ethylene methacrylic acid copolymer.
Described chloroprene rubber is the slow non-sulphur adjustment type chloroprene rubber of crystallization velocity, and mooney viscosity is 48 ± 5.
Described oxidation inhibitor is the composite of a kind of in phenolic antioxidant, both ester kind antioxidants or two kinds.The composite mass ratio of this phenolic antioxidant, ester kind antioxidant is (0.5-3): (0.5-3).
Described phenolic antioxidant is one or more composite in following material: 2,4,6-tri-butyl-phenol (oxidation inhibitor 246); Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010).
Described ester kind antioxidant is one or more composite in following material: β-positive octadecanol ester (antioxidant 1076) of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid; Tyox B (anti-oxidant DLTP); Three [2.4-di-tert-butyl-phenyl] phosphorous acid ester (irgasfos 168); Triphenyl phosphite (TPP).
Described softening agent is ester plasticizer, one or more composite in following material: dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DBP), dioctyl sebacate (DOS).
The composite mass ratio of above-mentioned dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DBP), dioctyl sebacate (DOS) three is (1-15): (1-15): the plasticizer of (1-15).
Above-mentioned substance all can be commercially.
The preparation method of above-mentioned radiation crosslinking chloroprene rubber heat-shrinkage material comprises the following steps:
Step 1: take polyolefin substrate 100 parts, chloroprene rubber 5-20 part, chlorinatedpolyethylene 5-20 part, oxidation inhibitor 0.5-3 part, softening agent 1-15 part, Masterbatch 1-5 part according to parts by weight, at room temperature fully mix;
Step 2: the broken rear twin screw extruder of material cooling step 1 mixed extrudes tie rod, water-cooled in 130 DEG C of-180 DEG C of temperature ranges, air-dry, pelletizing;
Step 3: above-mentioned material grain is extruded into tubulose at 130 DEG C of-180 DEG C of temperature;
Step 4: by aforementioned tubes through gamma-rays or rumbatron radiation, radiation dose 80-200KGY;
Step 5: then at 100-200 DEG C of temperature, aforementioned tubes expansion is stretched to 0.5-3 doubly heat-shrink tube.
Cross-linking radiation chloroprene rubber heat-shrinkage material of the present invention can be used for making various thermal contraction device, comprises heat-shrink tube, can be low temperature resistant-70 DEG C, and oil resistant, heat aging property are good.The present invention expands kind and the range of application of thermal contraction product, has also opened up the new application space of chloroprene rubber simultaneously.Aforementioned tubes performance is good, and preparation method is simple, is suitable for suitability for industrialized production.
Technical scheme of the present invention is set forth further below by preparation embodiment.
Preparation embodiment 1
According to the form below gets various component:
according to proportioning above, above-mentioned substance is mixed in Banbury mixer (mixture is 20kg altogether).
Then at the temperature of 160 DEG C, tie rod, water-cooled, air-dry, pelletizing is extruded through twin screw extruder.
Again through being extruded as tubing, through rumbatron radiation 100KGY, then become heat-shrinkable tube by expansion 2 times.Measure as follows:
Preparation embodiment 2
According to the form below gets various component:
According to proportioning above, above-mentioned substance is mixed in Banbury mixer (mixture is 20kg altogether).
Then at the temperature of 130 DEG C, tie rod, water-cooled, air-dry, pelletizing is extruded through twin screw extruder.
Again through being extruded as tubing, through rumbatron radiation 120KGY, then become heat-shrinkable tube by expansion 2 times.Measure as follows:
Preparation embodiment 3
According to the form below gets various component:
According to proportioning above, above-mentioned substance is mixed in Banbury mixer (mixture is 20kg altogether).
Then at the temperature of 180 DEG C, tie rod, water-cooled, air-dry, pelletizing is extruded through twin screw extruder.
Again through being extruded as tubing, through rumbatron radiation 80KGY, then become heat-shrinkable tube by expansion 2 times.Measure as follows:
Preparation embodiment 4
According to the form below gets various component:
according to proportioning above, above-mentioned substance is mixed in Banbury mixer (mixture is 20kg altogether).
Then at the temperature of 160 DEG C, tie rod, water-cooled, air-dry, pelletizing is extruded through twin screw extruder.
Again through being extruded as tubing, through rumbatron radiation 200KGY, then become heat-shrinkable tube by expansion 3 times.Measure as follows:
Preparation embodiment 5
According to the form below gets various component:
according to proportioning above, above-mentioned substance is mixed in Banbury mixer (mixture is 20kg altogether).
Then at the temperature of 180 DEG C, tie rod, water-cooled, air-dry, pelletizing is extruded through twin screw extruder.
Again through being extruded as tubing, through rumbatron radiation 130KGY, then become heat-shrinkable tube by expansion 2 times.Measure as follows:
Claims (1)
1. a radiation crosslinking chloroprene rubber heat-shrinkage material, it is made up of the following component with weight parts:
Polyolefin substrate 100 parts;
Chloroprene rubber 5-20 part;
Chlorinatedpolyethylene 5-20 part;
Oxidation inhibitor 0.5-3 part;
Softening agent 1-15 part;
Masterbatch 1-5 part;
Described polyolefin substrate is one or more the mixture in following material: polyethylene; Ethylene-vinyl acetate copolymer.
2. radiation crosslinking chloroprene rubber heat-shrinkage material according to claim 1, is characterized in that: described chloroprene rubber is the slow non-sulphur adjustment type chloroprene rubber of crystallization velocity, and mooney viscosity is 48 ± 5.
3. radiation crosslinking chloroprene rubber heat-shrinkage material according to claim 1, it is characterized in that: described oxidation inhibitor is the composite of a kind of in phenolic antioxidant, both ester kind antioxidants or two kinds, the composite mass ratio of this phenolic antioxidant, ester kind antioxidant is (0.5-3): (0.5-3);
Described phenolic antioxidant is one or more composite in following material: 2,4,6-tri-butyl-phenol; Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Described ester kind antioxidant is one or more composite in following material: β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid; Tyox B; Three [2.4-di-tert-butyl-phenyl] phosphorous acid ester; Triphenyl phosphite.
4. radiation crosslinking chloroprene rubber heat-shrinkage material according to claim 1, it is characterized in that: described softening agent is ester plasticizer, is one or more composite in following material: dioctyl phthalate (DOP), dibutyl phthalate, dioctyl sebacate;
The composite mass ratio of above-mentioned dioctyl phthalate (DOP), dibutyl phthalate, dioctyl sebacate three is (1-15): (1-15): (1-15).
5. the preparation method of radiation crosslinking chloroprene rubber heat-shrinkage material as claimed in claim 1, it is characterized in that, it comprises the following steps:
Step 1: take polyolefin substrate 100 parts, chloroprene rubber 5-20 part, chlorinatedpolyethylene 5-20 part, oxidation inhibitor 0.5-3 part, softening agent 1-15 part, Masterbatch 1-5 part according to parts by weight, at room temperature fully mix;
Step 2: the broken rear twin screw extruder of material cooling step 1 mixed extrudes tie rod, water-cooled in 130 DEG C of-180 DEG C of temperature ranges, air-dry, pelletizing;
Step 3: above-mentioned material grain is extruded into tubulose at 130 DEG C of-180 DEG C of temperature;
Step 4: by aforementioned tubes through gamma-rays or rumbatron radiation, radiation dose 80-200KGY;
Step 5: then at 100-200 DEG C of temperature, aforementioned tubes expansion is stretched to 0.5-3 doubly heat-shrink tube.
6. the preparation method of radiation crosslinking chloroprene rubber heat-shrinkage material according to claim 5, is characterized in that, described chloroprene rubber is the slow non-sulphur adjustment type chloroprene rubber of crystallization velocity, and mooney viscosity is 48 ± 5.
7. the preparation method of radiation crosslinking chloroprene rubber heat-shrinkage material according to claim 5, it is characterized in that, described oxidation inhibitor is the composite of a kind of in phenolic antioxidant, both ester kind antioxidants or two kinds, and the composite mass ratio of this phenolic antioxidant, ester kind antioxidant is (0.5-3): (0.5-3);
Described phenolic antioxidant is one or more composite in following material: 2,4,6-tri-butyl-phenol; Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Described ester kind antioxidant is one or more composite in following material: β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid; Tyox B; Three [2.4-di-tert-butyl-phenyl] phosphorous acid ester; Triphenyl phosphite.
8. the preparation method of radiation crosslinking chloroprene rubber heat-shrinkage material according to claim 5, it is characterized in that, described softening agent is ester plasticizer, is one or more composite in following material: dioctyl phthalate (DOP), dibutyl phthalate, dioctyl sebacate;
The composite mass ratio of above-mentioned dioctyl phthalate (DOP), dibutyl phthalate, dioctyl sebacate three is (1-15): (1-15): (1-15).
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Effective date of registration: 20180328 Address after: 523770 Guangdong province Dongguan city Dalang town Fumin Industrial Park Po Po Industrial Zone two Co-patentee after: Changyuan electronic (Group) Co., Ltd. Patentee after: Changyuan Electronics (Dongguan) Co., Ltd. Co-patentee after: Shanghai Changyuan Electronic Material Co., Ltd. Co-patentee after: Tianjin Changyuan Electronic Material Co., Ltd. Address before: 523770 Guangdong province Dongguan city Dalang town Fumin Industrial Park Po Po Industrial Zone two Co-patentee before: Changyuan electronic (Group) Co., Ltd. Patentee before: Changyuan Electronics (Dongguan) Co., Ltd. Co-patentee before: Shanghai Changyuan Electronic Material Co., Ltd. Co-patentee before: Tianjin Changyuan Electronic Material Co., Ltd. Co-patentee before: ChangYuan Group Ltd. |