CN108219325A - A kind of graphene Reinforced PVC composite pipe and preparation method thereof - Google Patents
A kind of graphene Reinforced PVC composite pipe and preparation method thereof Download PDFInfo
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- CN108219325A CN108219325A CN201810179342.2A CN201810179342A CN108219325A CN 108219325 A CN108219325 A CN 108219325A CN 201810179342 A CN201810179342 A CN 201810179342A CN 108219325 A CN108219325 A CN 108219325A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/18—Applications used for pipes
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Abstract
The present invention relates to a kind of graphene Reinforced PVC composite pipes and preparation method thereof；A kind of graphene Reinforced PVC composite pipe proposed by the present invention and preparation method thereof its composition of raw materials includes the component of following parts by weight meter：100 200 parts of PVC, 26 parts of stabilizer, 12 parts of in-lubricant, 12 parts of external lubricant, 4 12 parts of modified graphene, 80 120 parts of filler material, 25 parts of antioxidant, 6 20 parts of toughener are plasticized 26 parts of accelerating agent；Intensity present invention aim to address PVC multiple tubes at present on the market is relatively low, service life is short and easily bursts under lower temperature conditions, the problems such as being easily deformed under higher temperature conditions, the present invention is the performance for carrying out Reinforced PVC multiple tube by using modified graphene and carries out extending its service life by special antioxidant.
Description
Technical field
The invention belongs to polymer modification and preparation field fields, and in particular to a kind of graphene Reinforced PVC is compound
Tubing and preparation method thereof.
Background technology
The a little year development of use of Chinese PVC pipe are very fast, more than 8% arrival per annual increment rate, and the increase needed every year
Rate is 2%.In plastic pipe, for PVC pipe dosage one to holding a safe lead, it is widely applied to water supply and sewerage pipeline, is each
One of most widely used material in class tube material, on the other hand, the use of PVC pipe and our life are closely bound up,
The quality of PVC pipe is very significant considering that the raising of our quality of life, for now many PVC pipe
Influence for temperature is very big, the problem of often easily explosion under relatively low temperature condition, and higher conditions of problems
Lower the problems such as easily softening, the use scope for resulting in PVC pipe is restricted, and this patent just can be good at solving
PVC pipe in terms of mechanical property the problem of.
In patent CN107337870A, disclose a kind of interior decoration pvc pipe, the interior decoration pvc pipe by
Following parts by weight material is made：200-500 parts of PVC granule, ceramic 20-50 parts of grain, 50-100 parts of epoxy resin, phenolic resin
30-80 parts, 20-50 parts of organic siliconresin, 20-40 parts of nano-titanium oxide, 8-15 parts of nano zine oxide, 15-35 parts of polyester fiber,
30-40 parts of dimethicone, 3-12 parts of tungsten powder, 5-12 parts of nano zircite, 5-8 parts of carbon nanotube etc.；By extrusion molding and
It prepares, although the pvc pipe which prepares significantly improves the fusing point of pvc pipe, burning point makes flame retardant property of the invention and resistance to
High-temperature behavior significantly improves, but its it is relatively low temperature resistant for poor-performing, and used phenolic resin therefore its application range
It is more narrow, it is only used for sewage class.On the other hand, pvc pipe compression strength and tensile strength are relatively low；
In patent CN105802078A, the pvc pipe and its preparation process of a kind of high intensity are disclosed, pvc pipe is by following
The each group of weight proportion is grouped as, and polyvinyl chloride is 60~70 parts, and natural rubber is 2~5 parts, and dimethicone is 2~3 parts,
Kaolin is 3~5 parts, and clay is 5~9 parts, and antioxidant 264 is 2~3 parts, and magnesium hydroxide is 10~15 parts, and paraffin is 3~5
Part, titanium dioxide is 5~12 parts；The preparation method is that：By above-mentioned various raw materials successively Hybrid Heating, cooling after by squeeze
Press squeezes out.The method prepare pvc pipe comparatively its intensity be not it is very high, on the other hand its ageing-resistant performance relatively
Low, the service life of tubing is shorter；
In patent CN106674809A, a kind of pvc pipe and preparation method thereof, by weight number scale are disclosed, component is such as
Under：PVC100 parts, 10-20 parts of dioctyl phthalate, 2-4 parts of methanol, 10-20 parts of haloflex, calcium stearate 3-10
Part, 3-5 parts of paraffin, 2-4 parts of titanium dioxide, by mentioned component PVC, dioctyl phthalate, methanol, haloflex, tristearin
Sour calcium, paraffin, titanium dioxide are put into stirrer for mixing stirring according to said components, and then mixture is put into extruder and is prepared
Obtained from, the problems such as tubing its toughness which prepares is weaker, easy embrittlement, anti-aging property are poor and intensity is relatively low.
Invention content
In view of the above-mentioned analysis to the prior art, the present invention provides a kind of graphene Reinforced PVC composite pipe and its preparation
Method, the PVC composite pipe function admirables, intensity is high, it is corrosion-resistant, can be good at adapting to higher and lower temperature environment,
And preparation method is simple, suitable for mass producing and applying.
In order to achieve the above object, the present invention is achieved through the following technical solutions：
A kind of graphene Reinforced PVC composite pipe, the PVC composite pipes include following raw material group in terms of parts by weight
Into：100-200 parts of PVC, 2-6 parts of stabilizer, 1-2 parts of in-lubricant, 1-2 parts of external lubricant, 4-12 parts of modified graphene are filled out
80-120 parts of charge, 2-5 parts of antioxidant, 6-20 parts of toughener are plasticized 2-6 parts of accelerating agent.
Wherein, in terms of parts by weight, the PVC composite pipes mainly include following components：100 parts of PVC, stabilizer 2
Part, 2 parts of in-lubricant, 1 part of external lubricant, 10 parts of modified graphene, 80 parts of filler material, 2 parts of antioxidant, 6 parts of toughener, modeling
Change 3 parts of accelerating agent.
Preferably, the PVC is the PVC of SG-8 SG-5 models.
Preferably, the stabilizer is, the calcium stable agent of 20-40 parts of parts by weight meter, 40-60 parts of calcium zinc are steady
Determine agent, 12-20 parts of active calcium oxide mixture.
Preferably, the in-lubricant is, the peroxide polyethylene wax, 4-6 parts of tristearin of 2-8 parts of parts by weight meter
Sour sodium, 2-3 parts of zinc stearate, 3-4 parts of calcium stearate, 4-6 parts of stearate Type of Collective object are added in batch mixer and are carried out
Then mixing, control batch mixer temperature carry out mixing 3-5 minutes, institute are taken out after then carrying out cold mixed 2-5 minutes at 60-80 DEG C
It prepares.
Preferably, the external lubricant is, the PE- waxes of 2-10 parts of parts by weight meter, 1-5 parts of polyethylene wax,
3-5 parts of sorbic acid, 3-8 parts of haloflex are added in batch mixer and are mixed, and control batch mixer temperature at 60-80 DEG C,
Then mixing 3-5 minutes is carried out, after then carrying out cold mixed 2-5 minutes prepared by taking-up.
Preferably, the modified graphene is, the graphene that parts by weight are 10-20 parts is added in into the mixed of 5-10L
In material machine, then add 1-5 parts hexamethylene diisocyanate or polyisocyanic acid polymethylene polyphenyl ester, 1-2 parts
The peroxide ethylene waxes of 3-5 parts of organotin, at 60-80 DEG C, rotating speed 120-300 turns control temperature of reaction kettle, then carries out reaction 1-
After 1.5 hours, after temperature of reaction kettle is increased 2-5 DEG C, add in 1-2 part of dibenzoyl peroxide and then carry out reacting 1-2 small
Shi Hou, then taken out after keeping the temperature 1 hour, what is obtained is exactly modified graphene.
Preferably, the filler material is activated Calcium carbonate, activated silica diatomaceous earth, active high-level laterite, active coal ash etc.
One kind in substance.
Preferably, the antioxidant is, by ordinary titanium powder, adds in baking oven and dried, drying temperature
At 100-200 DEG C, time 1-2 hour adds in ball mill after drying and is ground, and granular size takes when being 500-100 mesh
Go out, then add in the titanium dioxide after the grinding of 10-20 parts of parts by weight meter in batch mixer, then adding in 1-5 parts of 2-
Hydroxyl -4- oxy-octyl benzophenones, 2-3 parts of 2- (2 '-hydroxyl -3 ', 5 '-two tertiary phenyl) -5- chlorinations benzotriazole, 3-5
Then temperature is controlled and is taken out after carrying out mixing 10-20 minutes at 50-80 DEG C, obtains antioxidant by the peroxide ethylene waxes of part.
Preferably, the toughener is, the rubber powder of 20-50 parts of mass fraction meter, 2-8 parts of high glue powder,
10-15 parts of ABS is mixed, obtained mixture.
Preferably, the plasticizing accelerating agent is, the polymethyl methacrylate of 2-5 parts of parts by weight meter, 3-4 parts
Polyethyl methacrylate, 5-6 parts of polyacrylate, 3-6 parts of styrene mixed, obtained mixture.
The present invention also provides the preparation methods of PVC composite pipes, include the following steps：
(1) mixing of raw material
By PVC, stabilizer, in-lubricant, external lubricant, filler material, add in batch mixer and mixed by above-mentioned mass ratio
It closes, control batch mixer temperature carries out mixed on low speed 1-2 minutes first at 60-80 DEG C, is then turned on high mixed, batch mixing 5-10 minutes
Successively antioxidant, toughener, plasticizing accelerating agent, modified graphene are added in batch mixer and carry out mixing 1-3 in mass ratio afterwards
Minute, material is put into cold mixer and is mixed, mixing is taken out after 5-10 minutes, obtains PVC multiple tube mixtures.
(2) preparation of PVC multiple tubes
Uniformly mixed PVC multiple tubes mixed material is added in, heat fusing extrusion is carried out in double screw extruder, obtain PVC
Multiple tube；Its continuous extrusion industrial condition such as following table：
(3) it packs
PVC multiple tubes in step (2) are packed, and are exactly the preparation method of graphene Reinforced PVC multiple tube.
Beneficial to benefit
(1) PVC multiple tubes its intensity height prepared by the present invention, the intensity of graphene is very high, and the present invention is logical
It is increased to carry out to cross modified graphene, and the characteristic of graphene is utilized well, improves the strong of PVC multiple tubes well
Degree.
(2) the PVC multiple tubes prepared by the present invention, the influence that temperature is used for is smaller, and use temperature range can
With -60 DEG C -70 DEG C without occur explosion or deformation a problem that.
(3) the PVC multiple tubes prepared by the present invention use extraordinary antioxidant, and ageing-resistant performance is strong,
So as to ensure that the service life of the PVC multiple tubes is longer.
(4) preparation process of PVC multiple tubes of the invention is simple, industrialized production easy to implement.
Specific embodiment
In order to make the purpose of the present invention, technical solution and advantageous effect clearer, below in conjunction with experimental data, to this
The preferred embodiment of invention is described in detail, to facilitate the technical staff to understand.
Embodiment 1
A kind of graphene Reinforced PVC composite pipe, the PVC composite pipes include following raw material group in terms of parts by weight
Into：100 parts of PVC, 2 parts of stabilizer, 1 part of in-lubricant, 1 part of external lubricant, 12 parts of modified graphene, 80 parts of filler material, antioxygen
5 parts of agent, 20 parts of toughener are plasticized 6 parts of accelerating agent.
Wherein, the PVC is the PVC of SG-8 SG-5 models.
Wherein, the stabilizer is that the calcium stable agent of 20-40 parts of parts by weight meter, 40-60 parts of calcium zinc are stablized
Agent, the mixture of 12-20 parts of active calcium oxide.
Wherein, the in-lubricant is the peroxide polyethylene wax, 4-6 parts of stearic acid of 2-8 parts of parts by weight meter
Sodium, 2-3 parts of zinc stearate, 3-4 parts of calcium stearate, 4-6 parts of stearate Type of Collective object are added in batch mixer and are mixed
It closes, then control batch mixer temperature carries out mixing 3-5 minutes, taken out after then carrying out cold mixed 2-5 minutes made at 60-80 DEG C
Standby.
Wherein, the external lubricant is, the PE- waxes of 2-10 parts of parts by weight meter, 1-5 parts of polyethylene wax, 3-5 parts
Sorbic acid, 3-8 parts of haloflex add in batch mixer and mixed, control batch mixer temperature is at 60-80 DEG C, Ran Houjin
Row mixing 3-5 minutes, after then carrying out cold mixed 2-5 minutes prepared by taking-up.
Wherein, the modified graphene is that the graphene that parts by weight are 10-20 parts is added in the batch mixer of 5-10L
In, then add 1-5 parts of hexamethylene diisocyanate or polyisocyanic acid polymethylene polyphenyl ester, 1-2 parts organic
The peroxide ethylene waxes of 3-5 parts of tin, at 60-80 DEG C, rotating speed 120-300 turns control temperature of reaction kettle, and it is small then to carry out reaction 1-1.5
Shi Hou after temperature of reaction kettle is increased 2-5 DEG C, adds in 1-2 parts of dibenzoyl peroxide and then carries out after reacting 1-2 hours,
It is taken out after keeping the temperature 1 hour again, what is obtained is exactly modified graphene.
Wherein, the filler material is activated Calcium carbonate, the substances such as activated silica diatomaceous earth, active high-level laterite, active coal ash
In one kind.
Wherein, the antioxidant is, by ordinary titanium powder, to add in baking oven and dried, drying temperature exists
100-200 DEG C, time 1-2 hour adds in ball mill after drying and is ground, and granular size is taken out when being 500-100 mesh,
Then the titanium dioxide after the grinding of 10-20 parts of parts by weight meter is added in batch mixer, is then adding in 1-5 parts of 2- hydroxyls
Base -4- oxy-octyl benzophenones, 2-3 parts of 2- (2 '-hydroxyl -3 ', 5 '-two tertiary phenyl) -5- chlorinations benzotriazole, 3-5 parts
Peroxide ethylene waxes, then by temperature control 50-80 DEG C carry out mixing 10-20 minutes after take out, obtain antioxidant.
Wherein, the toughener is the rubber powder, 2-8 parts of high glue powder, 10-15 of 20-50 parts of mass fraction meter
The ABS of part is mixed, obtained mixture.
Wherein, the plasticizing accelerating agent is, the polymethyl methacrylate of 2-5 parts of parts by weight meter, 3-4 parts poly-
Ethyl methacrylate, 5-6 parts of polyacrylate, 3-6 parts of styrene are mixed, obtained mixture.
The present invention also provides the preparation methods of PVC composite pipes, include the following steps：
(1) mixing of raw material
It by PVC, stabilizer, in-lubricant, external lubricant, filler material, adds in batch mixer and is mixed, control batch mixer
Temperature carries out mixed on low speed 1-2 minute first at 60-80 DEG C, be then turned on it is high mix, batch mixing after 5-10 minutes by antioxidant,
Toughener, plasticizing accelerating agent, modified graphene add in batch mixer according to sequencing and carry out mixing 1-3 minutes, and material is put
Enter in cold mixer and mixed, mixing is taken out after 5-10 minutes, obtains PVC multiple tube mixtures；
(2) preparation of PVC multiple tubes
Uniformly mixed PVC multiple tubes mixed material is added in, heat fusing extrusion is carried out in double screw extruder, obtain PVC
Multiple tube continuously squeezes out industrial condition such as following table：
(3) it packs
PVC multiple tubes in step (2) are packed, and are exactly the preparation method of graphene Reinforced PVC multiple tube.
Embodiment 2
A kind of graphene Reinforced PVC composite pipe, the PVC composite pipes include following raw material group in terms of parts by weight
Into：120 parts of PVC, 2 parts of stabilizer, 1.2 parts of in-lubricant, external lubricant 1
Part, 10 parts of modified graphene, 100 parts of filler material, 5 parts of antioxidant, 15 parts of toughener, 5 parts of accelerating agent of plasticizing.
Wherein, the PVC is the PVC of SG-8 SG-5 models.
Wherein, the stabilizer is that the calcium stable agent of 20-40 parts of parts by weight meter, 40-60 parts of calcium zinc are stablized
Agent, the mixture of 12-20 parts of active calcium oxide.
Wherein, the in-lubricant is the peroxide polyethylene wax, 4-6 parts of stearic acid of 2-8 parts of parts by weight meter
Sodium, 2-3 parts of zinc stearate, 3-4 parts of calcium stearate, 4-6 parts of stearate Type of Collective object are added in batch mixer and are mixed
It closes, then control batch mixer temperature carries out mixing 3-5 minutes, taken out after then carrying out cold mixed 2-5 minutes made at 60-80 DEG C
Standby.
Wherein, the external lubricant is, the PE- waxes of 2-10 parts of parts by weight meter, 1-5 parts of polyethylene wax, 3-5 parts
Sorbic acid, 3-8 parts of haloflex add in batch mixer and mixed, control batch mixer temperature is at 60-80 DEG C, Ran Houjin
Row mixing 3-5 minutes, after then carrying out cold mixed 2-5 minutes prepared by taking-up.
Wherein, the modified graphene is that the graphene that parts by weight are 10-20 parts is added in the batch mixer of 5-10L
In, then add 1-5 parts of hexamethylene diisocyanate or polyisocyanic acid polymethylene polyphenyl ester, 1-2 parts organic
The peroxide ethylene waxes of 3-5 parts of tin, at 60-80 DEG C, rotating speed 120-300 turns control temperature of reaction kettle, and it is small then to carry out reaction 1-1.5
Shi Hou after temperature of reaction kettle is increased 2-5 DEG C, adds in 1-2 parts of dibenzoyl peroxide and then carries out after reacting 1-2 hours,
It is taken out after keeping the temperature 1 hour again, what is obtained is exactly modified graphene.
Wherein, the filler material is activated Calcium carbonate, the substances such as activated silica diatomaceous earth, active high-level laterite, active coal ash
In one kind.
Wherein, the antioxidant is, by ordinary titanium powder, to add in baking oven and dried, drying temperature exists
100-200 DEG C, time 1-2 hour adds in ball mill after drying and is ground, and granular size is taken out when being 500-100 mesh,
Then the titanium dioxide after the grinding of 10-20 parts of parts by weight meter is added in batch mixer, is then adding in 1-5 parts of 2- hydroxyls
Base -4- oxy-octyl benzophenones, 2-3 parts of 2- (2 '-hydroxyl -3 ', 5 '-two tertiary phenyl) -5- chlorinations benzotriazole, 3-5 parts
Peroxide ethylene waxes, then by temperature control 50-80 DEG C carry out mixing 10-20 minutes after take out, obtain antioxidant.
Wherein, the toughener is the rubber powder, 2-8 parts of high glue powder, 10-15 of 20-50 parts of mass fraction meter
The ABS of part is mixed, obtained mixture.
Wherein, the plasticizing accelerating agent is, the polymethyl methacrylate of 2-5 parts of parts by weight meter, 3-4 parts poly-
Ethyl methacrylate, 5-6 parts of polyacrylate, 3-6 parts of styrene are mixed, obtained mixture.
The present invention also provides the preparation methods of PVC composite pipes, include the following steps：
(1) mixing of raw material
It by PVC, stabilizer, in-lubricant, external lubricant, filler material, adds in batch mixer and is mixed, control batch mixer
Temperature carries out mixed on low speed 1-2 minute first at 60-80 DEG C, be then turned on it is high mix, batch mixing after 5-10 minutes by antioxidant,
Toughener, plasticizing accelerating agent, modified graphene add in batch mixer according to sequencing and carry out mixing 1-3 minutes, and material is put
Enter in cold mixer and mixed, mixing is taken out after 5-10 minutes, obtains PVC multiple tube mixtures；
(2) preparation of PVC multiple tubes
Uniformly mixed PVC multiple tubes mixed material is added in, heat fusing extrusion is carried out in double screw extruder, obtain PVC
Multiple tube continuously squeezes out industrial condition such as following table：
(3) it packs
PVC multiple tubes in step (2) are packed, and are exactly the preparation method of graphene Reinforced PVC multiple tube.
Embodiment 3
A kind of graphene Reinforced PVC composite pipe, the PVC composite pipes include following raw material group in terms of parts by weight
Into：150 parts of PVC, 2.5 parts of stabilizer, 1.2 parts of in-lubricant, 1 part of external lubricant, 8 parts of modified graphene, 100 parts of filler material,
4 parts of antioxidant, 14 parts of toughener are plasticized 5 parts of accelerating agent.
Wherein, the PVC is the PVC of SG-8 SG-5 models.
Wherein, the stabilizer is that the calcium stable agent of 20-40 parts of parts by weight meter, 40-60 parts of calcium zinc are stablized
Agent, the mixture of 12-20 parts of active calcium oxide.
Wherein, the in-lubricant is the peroxide polyethylene wax, 4-6 parts of stearic acid of 2-8 parts of parts by weight meter
Sodium, 2-3 parts of zinc stearate, 3-4 parts of calcium stearate, 4-6 parts of stearate Type of Collective object are added in batch mixer and are mixed
It closes, then control batch mixer temperature carries out mixing 3-5 minutes, taken out after then carrying out cold mixed 2-5 minutes made at 60-80 DEG C
Standby.
Wherein, the external lubricant is, the PE- waxes of 2-10 parts of parts by weight meter, 1-5 parts of polyethylene wax, 3-5 parts
Sorbic acid, 3-8 parts of haloflex add in batch mixer and mixed, control batch mixer temperature is at 60-80 DEG C, Ran Houjin
Row mixing 3-5 minutes, after then carrying out cold mixed 2-5 minutes prepared by taking-up.
Wherein, the modified graphene is that the graphene that parts by weight are 10-20 parts is added in the batch mixer of 5-10L
In, then add 1-5 parts of hexamethylene diisocyanate or polyisocyanic acid polymethylene polyphenyl ester, 1-2 parts organic
The peroxide ethylene waxes of 3-5 parts of tin, at 60-80 DEG C, rotating speed 120-300 turns control temperature of reaction kettle, and it is small then to carry out reaction 1-1.5
Shi Hou after temperature of reaction kettle is increased 2-5 DEG C, adds in 1-2 parts of dibenzoyl peroxide and then carries out after reacting 1-2 hours,
It is taken out after keeping the temperature 1 hour again, what is obtained is exactly modified graphene.
Wherein, the filler material is activated Calcium carbonate, the substances such as activated silica diatomaceous earth, active high-level laterite, active coal ash
In one kind.
Wherein, the antioxidant is, by ordinary titanium powder, to add in baking oven and dried, drying temperature exists
100-200 DEG C, time 1-2 hour adds in ball mill after drying and is ground, and granular size is taken out when being 500-100 mesh,
Then the titanium dioxide after the grinding of 10-20 parts of parts by weight meter is added in batch mixer, is then adding in 1-5 parts of 2- hydroxyls
Base -4- oxy-octyl benzophenones, 2-3 parts of 2- (2 '-hydroxyl -3 ', 5 '-two tertiary phenyl) -5- chlorinations benzotriazole, 3-5 parts
Peroxide ethylene waxes, then by temperature control 50-80 DEG C carry out mixing 10-20 minutes after take out, obtain antioxidant.
Wherein, the toughener is the rubber powder, 2-8 parts of high glue powder, 10-15 of 20-50 parts of mass fraction meter
The ABS of part is mixed, obtained mixture.
Wherein, the plasticizing accelerating agent is, the polymethyl methacrylate of 2-5 parts of parts by weight meter, 3-4 parts poly-
Ethyl methacrylate, 5-6 parts of polyacrylate, 3-6 parts of styrene are mixed, obtained mixture.
The present invention also provides the preparation methods of PVC composite pipes, include the following steps：
(1) mixing of raw material
It by PVC, stabilizer, in-lubricant, external lubricant, filler material, adds in batch mixer and is mixed, control batch mixer
Temperature carries out mixed on low speed 1-2 minute first at 60-80 DEG C, be then turned on it is high mix, batch mixing after 5-10 minutes by antioxidant,
Toughener, plasticizing accelerating agent, modified graphene add in batch mixer according to sequencing and carry out mixing 1-3 minutes, and material is put
Enter in cold mixer and mixed, mixing is taken out after 5-10 minutes, obtains PVC multiple tube mixtures；
(2) preparation of PVC multiple tubes
Uniformly mixed PVC multiple tubes mixed material is added in, heat fusing extrusion is carried out in double screw extruder, obtain PVC
Multiple tube continuously squeezes out industrial condition such as following table：
(3) it packs
PVC multiple tubes in step (2) are packed, and are exactly the preparation method of graphene Reinforced PVC multiple tube.
Embodiment 4
A kind of graphene Reinforced PVC composite pipe, the PVC composite pipes include following raw material group in terms of parts by weight
Into：200 parts of PVC, 2 parts of stabilizer, 1.2 parts of in-lubricant, 1 part of external lubricant, 4 parts of modified graphene, 120 parts of filler material resist
5 parts of oxidant, 12 parts of toughener are plasticized 5 parts of accelerating agent.
Wherein, the PVC is the PVC of SG-8 SG-5 models.
Wherein, the stabilizer is that the calcium stable agent of 20-40 parts of parts by weight meter, 40-60 parts of calcium zinc are stablized
Agent, the mixture of 12-20 parts of active calcium oxide.
Wherein, the in-lubricant is the peroxide polyethylene wax, 4-6 parts of stearic acid of 2-8 parts of parts by weight meter
Sodium, 2-3 parts of zinc stearate, 3-4 parts of calcium stearate, 4-6 parts of stearate Type of Collective object are added in batch mixer and are mixed
It closes, then control batch mixer temperature carries out mixing 3-5 minutes, taken out after then carrying out cold mixed 2-5 minutes made at 60-80 DEG C
Standby.
Wherein, the external lubricant is, the PE- waxes of 2-10 parts of parts by weight meter, 1-5 parts of polyethylene wax, 3-5 parts
Sorbic acid, 3-8 parts of haloflex add in batch mixer and mixed, control batch mixer temperature is at 60-80 DEG C, Ran Houjin
Row mixing 3-5 minutes, after then carrying out cold mixed 2-5 minutes prepared by taking-up.
Wherein, the modified graphene is that the graphene that parts by weight are 10-20 parts is added in the batch mixer of 5-10L
In, then add 1-5 parts of hexamethylene diisocyanate or polyisocyanic acid polymethylene polyphenyl ester, 1-2 parts organic
The peroxide ethylene waxes of 3-5 parts of tin, at 60-80 DEG C, rotating speed 120-300 turns control temperature of reaction kettle, and it is small then to carry out reaction 1-1.5
Shi Hou after temperature of reaction kettle is increased 2-5 DEG C, adds in 1-2 parts of dibenzoyl peroxide and then carries out after reacting 1-2 hours,
It is taken out after keeping the temperature 1 hour again, what is obtained is exactly modified graphene.
Wherein, the filler material is activated Calcium carbonate, the substances such as activated silica diatomaceous earth, active high-level laterite, active coal ash
In one kind.
Wherein, the antioxidant is, by ordinary titanium powder, to add in baking oven and dried, drying temperature exists
100-200 DEG C, time 1-2 hour adds in ball mill after drying and is ground, and granular size is taken out when being 500-100 mesh,
Then the titanium dioxide after the grinding of 10-20 parts of parts by weight meter is added in batch mixer, is then adding in 1-5 parts of 2- hydroxyls
Base -4- oxy-octyl benzophenones, 2-3 parts of 2- (2 '-hydroxyl -3 ', 5 '-two tertiary phenyl) -5- chlorinations benzotriazole, 3-5 parts
Peroxide ethylene waxes, then by temperature control 50-80 DEG C carry out mixing 10-20 minutes after take out, obtain antioxidant.
Wherein, the toughener is the rubber powder, 2-8 parts of high glue powder, 10-15 of 20-50 parts of mass fraction meter
The ABS of part is mixed, obtained mixture.
Wherein, the plasticizing accelerating agent is, the polymethyl methacrylate of 2-5 parts of parts by weight meter, 3-4 parts poly-
Ethyl methacrylate, 5-6 parts of polyacrylate, 3-6 parts of styrene are mixed, obtained mixture.
The present invention also provides the preparation methods of PVC composite pipes, include the following steps：
(1) mixing of raw material
It by PVC, stabilizer, in-lubricant, external lubricant, filler material, adds in batch mixer and is mixed, control batch mixer
Temperature carries out mixed on low speed 1-2 minute first at 60-80 DEG C, be then turned on it is high mix, batch mixing after 5-10 minutes by antioxidant,
Toughener, plasticizing accelerating agent, modified graphene add in batch mixer according to sequencing and carry out mixing 1-3 minutes, and material is put
Enter in cold mixer and mixed, mixing is taken out after 5-10 minutes, obtains PVC multiple tube mixtures；
(2) preparation of PVC multiple tubes
Uniformly mixed PVC multiple tubes mixed material is added in, heat fusing extrusion is carried out in double screw extruder, obtain PVC
Multiple tube continuously squeezes out industrial condition such as following table：
(3) it packs
PVC multiple tubes in step (2) are packed, and are exactly the preparation method of graphene Reinforced PVC multiple tube.
Comparison is with reference to 1
The PVC multiple tubes being prepared with reference to patent CN107337870A.
Comparison is with reference to 2
The PVC multiple tubes being prepared with reference to patent CN105802078A.
Comparison is with reference to 3
The PVC multiple tubes being prepared with reference to patent CN106674809A.
Comparison is with reference to 4
A kind of graphene Reinforced PVC composite pipe, it is different from embodiment 1, modified graphene is eliminated in this method, with
PVC composite pipes described in parts by weight meter are formed including following raw material：100 parts of PVC, 2 parts of stabilizer are 1 part of in-lubricant, outer
1 part of lubricant, 80 parts of filler material, 5 parts of antioxidant, 20 parts of toughener are plasticized 6 parts of accelerating agent.
Wherein, the PVC is the PVC of SG-8 SG-5 models.
Wherein, the stabilizer is that the calcium stable agent of 20-40 parts of parts by weight meter, 40-60 parts of calcium zinc are stablized
Agent, the mixture of 12-20 parts of active calcium oxide.
Wherein, the in-lubricant is the peroxide polyethylene wax, 4-6 parts of stearic acid of 2-8 parts of parts by weight meter
Sodium, 2-3 parts of zinc stearate, 3-4 parts of calcium stearate, 4-6 parts of stearate Type of Collective object are added in batch mixer and are mixed
It closes, then control batch mixer temperature carries out mixing 3-5 minutes, taken out after then carrying out cold mixed 2-5 minutes made at 60-80 DEG C
Standby.
Wherein, the external lubricant is, the PE- waxes of 2-10 parts of parts by weight meter, 1-5 parts of polyethylene wax, 3-5 parts
Sorbic acid, 3-8 parts of haloflex add in batch mixer and mixed, control batch mixer temperature is at 60-80 DEG C, Ran Houjin
Row mixing 3-5 minutes, after then carrying out cold mixed 2-5 minutes prepared by taking-up.
Wherein, the modified graphene is that the graphene that parts by weight are 10-20 parts is added in the batch mixer of 5-10L
In, then add 1-5 parts of hexamethylene diisocyanate or polyisocyanic acid polymethylene polyphenyl ester, 1-2 parts organic
The peroxide ethylene waxes of 3-5 parts of tin, at 60-80 DEG C, rotating speed 120-300 turns control temperature of reaction kettle, and it is small then to carry out reaction 1-1.5
Shi Hou after temperature of reaction kettle is increased 2-5 DEG C, adds in 1-2 parts of dibenzoyl peroxide and then carries out after reacting 1-2 hours,
It is taken out after keeping the temperature 1 hour again, what is obtained is exactly modified graphene.
Wherein, the filler material is activated Calcium carbonate, the substances such as activated silica diatomaceous earth, active high-level laterite, active coal ash
In one kind.
Wherein, the antioxidant is, by ordinary titanium powder, to add in baking oven and dried, drying temperature exists
100-200 DEG C, time 1-2 hour adds in ball mill after drying and is ground, and granular size is taken out when being 500-100 mesh,
Then the titanium dioxide after the grinding of 10-20 parts of parts by weight meter is added in batch mixer, is then adding in 1-5 parts of 2- hydroxyls
Base -4- oxy-octyl benzophenones, 2-3 parts of 2- (2 '-hydroxyl -3 ', 5 '-two tertiary phenyl) -5- chlorinations benzotriazole, 3-5 parts
Peroxide ethylene waxes, then by temperature control 50-80 DEG C carry out mixing 10-20 minutes after take out, obtain antioxidant.
Wherein, the toughener is the rubber powder, 2-8 parts of high glue powder, 10-15 of 20-50 parts of mass fraction meter
The ABS of part is mixed, obtained mixture.
Wherein, the plasticizing accelerating agent is, the polymethyl methacrylate of 2-5 parts of parts by weight meter, 3-4 parts poly-
Ethyl methacrylate, 5-6 parts of polyacrylate, 3-6 parts of styrene are mixed, obtained mixture.
The present invention also provides the preparation methods of PVC composite pipes, include the following steps：
(1) mixing of raw material
It by PVC, stabilizer, in-lubricant, external lubricant, filler material, adds in batch mixer and is mixed, control batch mixer
Temperature carries out mixed on low speed 1-2 minute first at 60-80 DEG C, be then turned on it is high mix, batch mixing after 5-10 minutes by antioxidant,
Toughener, plasticizing accelerating agent, modified graphene add in batch mixer according to sequencing and carry out mixing 1-3 minutes, and material is put
Enter in cold mixer and mixed, mixing is taken out after 5-10 minutes, obtains PVC multiple tube mixtures；
(2) preparation of PVC multiple tubes
Uniformly mixed PVC multiple tubes mixed material is added in, heat fusing extrusion is carried out in double screw extruder, obtain PVC
Multiple tube continuously squeezes out industrial condition such as following table：
(3) it packs
PVC multiple tubes in step (2) are packed, and are exactly the preparation method of graphene Reinforced PVC multiple tube.
Comparison is with reference to 5
A kind of graphene Reinforced PVC composite pipe, this step has lacked antioxidant compared with implementing 1, in terms of parts by weight
The PVC composite pipes are formed including following raw material：100 parts of PVC, 2 parts of stabilizer, 1 part of in-lubricant, 1 part of external lubricant,
12 parts of modified graphene, 80 parts of filler material, 20 parts of toughener are plasticized 6 parts of accelerating agent.
Wherein, the PVC is the PVC of SG-8 SG-5 models.
Wherein, the stabilizer is that the calcium stable agent of 20-40 parts of parts by weight meter, 40-60 parts of calcium zinc are stablized
Agent, the mixture of 12-20 parts of active calcium oxide.
Wherein, the in-lubricant is the peroxide polyethylene wax, 4-6 parts of stearic acid of 2-8 parts of parts by weight meter
Sodium, 2-3 parts of zinc stearate, 3-4 parts of calcium stearate, 4-6 parts of stearate Type of Collective object are added in batch mixer and are mixed
It closes, then control batch mixer temperature carries out mixing 3-5 minutes, taken out after then carrying out cold mixed 2-5 minutes made at 60-80 DEG C
Standby.
Wherein, the external lubricant is, the PE- waxes of 2-10 parts of parts by weight meter, 1-5 parts of polyethylene wax, 3-5 parts
Sorbic acid, 3-8 parts of haloflex add in batch mixer and mixed, control batch mixer temperature is at 60-80 DEG C, Ran Houjin
Row mixing 3-5 minutes, after then carrying out cold mixed 2-5 minutes prepared by taking-up.
Wherein, the modified graphene is that the graphene that parts by weight are 10-20 parts is added in the batch mixer of 5-10L
In, then add 1-5 parts of hexamethylene diisocyanate or polyisocyanic acid polymethylene polyphenyl ester, 1-2 parts organic
The peroxide ethylene waxes of 3-5 parts of tin, at 60-80 DEG C, rotating speed 120-300 turns control temperature of reaction kettle, and it is small then to carry out reaction 1-1.5
Shi Hou after temperature of reaction kettle is increased 2-5 DEG C, adds in 1-2 parts of dibenzoyl peroxide and then carries out after reacting 1-2 hours,
It is taken out after keeping the temperature 1 hour again, what is obtained is exactly modified graphene.
Wherein, the filler material is activated Calcium carbonate, the substances such as activated silica diatomaceous earth, active high-level laterite, active coal ash
In one kind.
Wherein, the antioxidant is, by ordinary titanium powder, to add in baking oven and dried, drying temperature exists
100-200 DEG C, time 1-2 hour adds in ball mill after drying and is ground, and granular size is taken out when being 500-100 mesh,
Then the titanium dioxide after the grinding of 10-20 parts of parts by weight meter is added in batch mixer, is then adding in 1-5 parts of 2- hydroxyls
Base -4- oxy-octyl benzophenones, 2-3 parts of 2- (2 '-hydroxyl -3 ', 5 '-two tertiary phenyl) -5- chlorinations benzotriazole, 3-5 parts
Peroxide ethylene waxes, then by temperature control 50-80 DEG C carry out mixing 10-20 minutes after take out, obtain antioxidant.
Wherein, the toughener is the rubber powder, 2-8 parts of high glue powder, 10-15 of 20-50 parts of mass fraction meter
The ABS of part is mixed, obtained mixture.
Wherein, the plasticizing accelerating agent is, the polymethyl methacrylate of 2-5 parts of parts by weight meter, 3-4 parts poly-
Ethyl methacrylate, 5-6 parts of polyacrylate, 3-6 parts of styrene are mixed, obtained mixture.
The present invention also provides the preparation methods of PVC composite pipes, include the following steps：
(1) mixing of raw material
It by PVC, stabilizer, in-lubricant, external lubricant, filler material, adds in batch mixer and is mixed, control batch mixer
Temperature carries out mixed on low speed 1-2 minute first at 60-80 DEG C, be then turned on it is high mix, batch mixing after 5-10 minutes by antioxidant,
Toughener, plasticizing accelerating agent, modified graphene add in batch mixer according to sequencing and carry out mixing 1-3 minutes, and material is put
Enter in cold mixer and mixed, mixing is taken out after 5-10 minutes, obtains PVC multiple tube mixtures；
(2) preparation of PVC multiple tubes
Uniformly mixed PVC multiple tubes mixed material is added in, heat fusing extrusion is carried out in double screw extruder, obtain PVC
Multiple tube.Its continuous extrusion industrial condition such as following table：
(3) it packs
PVC multiple tubes in step (2) are packed, and are exactly the preparation method of graphene Reinforced PVC multiple tube.
Experimental analysis：
(1) Mechanics Performance Testing
By PVC multiple tubes prepared by embodiment 1-4 and the PVC multiple tubes that control group is done, according to standard GB/T/
The requirement of T8804.1-88 and GB/T8805-88 and regulation test its tensile strength and the modulus of elasticity in static bending and compression strength carries out
Test, test result is as follows shown in table:
As seen from the above table, its intensity of PVC multiple tubes that prepared by the present invention is higher than pvc pipe intensity prepared by reference group 1-3,
Performance is relatively very excellent.And the discovery that can be apparent from by embodiment 1 and comparison reference group 4,5, modified graphene answer PVC
The performance for closing pipe has a great impact, and what oxidant influence the mechanical property of PVC multiple tubes without.
(2) PVC composite pipes heatproof is tested
By PVC multiple tubes prepared by embodiment 1-4 and the PVC multiple tubes that control group is done, according to standard GB/T/T8801-
2007 requirement and regulation carry out test of falling under different temperatures, and test article is respectively put into -40-50 DEG C not in test
In insulating box under the conditions of synthermal after 2 minutes, rapid to take out, then the level height of slave phase falls in the air, Ran Houguan
The pattern after it falls is examined, test observations are as shown in the table:
As seen from the above table, its intensity of PVC multiple tubes for preparing of the present invention is than the pvc pipe model of resistance to temperature prepared by reference group 1-3
It encloses relatively extensively, performance is relatively very excellent under low temperature and hot conditions.It and can be very by embodiment 1 and comparison reference group 4,5
It clearly finds, modified graphene has a great impact to the temperature resistant range of PVC multiple tubes, and antioxidant is to PVC multiple tubes
Temperature resistant range without what large effect.
(3) ageing-resistant performance is tested
By PVC multiple tubes prepared by embodiment 1-4 and the PVC multiple tubes that control group is done, according to national standard xenon arc lamp GB/
The requirement of T 16422.2-1999 carries out accelerated aging test performance test, observes its cosmetic variation, test result is as follows table
It is shown:
As seen from the above table, its intensity of PVC multiple tubes for preparing of the present invention than pvc pipe prepared by reference group 1-3 more resistant to aging,
Its ageing-resistant performance is preferable, its service life of covert explanation is longer.It and can be very clear by embodiment 1 and comparison reference group 4,5
Clear discovery, antioxidant has a great impact to the ageing-resistant performance of PVC multiple tubes, and modified graphene is to PVC multiple tubes
Ageing-resistant performance without what large effect.
Finally illustrate, preferred embodiment above is merely to illustrate technical scheme of the present invention and unrestricted, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, are limited without departing from claims of the present invention.
Claims (10)
1. a kind of graphene Reinforced PVC composite pipe, it is characterised in that：The graphene Reinforced PVC composite pipe it is main
Parts by weight of raw materials forms：100-200 parts of PVC, 2-6 parts of stabilizer, 1-2 parts of in-lubricant, 1-2 parts of external lubricant, modified stone
Black alkene 4-12 parts, 80-120 parts of filler material, 2-5 parts of antioxidant, 6-20 parts of toughener, 2-6 parts of accelerating agent of plasticizing.
2. graphene Reinforced PVC composite pipe according to claim 1, it is characterised in that：The stabilizer is to include：
Parts by weight are calculated as 20-40 parts of calcium stable agent, the mixing of 40-60 parts of calcium zinc stabilizer, 12-20 parts of active calcium oxide
Object.
3. graphene Reinforced PVC composite pipe according to claim 1, it is characterised in that：The in-lubricant includes：
Parts by weight be calculated as 2-8 parts peroxide polyethylene wax, 4-6 parts of odium stearate, 2-3 parts of zinc stearate, 3-4 parts of stearic acid
Calcium, 4-6 parts of stearate Type of Collective object is added in batch mixer and is mixed, and control batch mixer temperature is at 60-80 DEG C, then
Mixing 3-5 minutes is carried out, mixture obtained by taking-up is prepared after then carrying out cold mixed 2-5 minutes.
4. graphene Reinforced PVC composite pipe according to claim 1, it is characterised in that：The external lubricant includes：
Parts by weight be calculated as 2-10 parts PE- waxes, 1-5 parts of polyethylene wax, 3-5 parts of sorbic acid, 3-8 parts haloflex add in
It is mixed in batch mixer, then control batch mixer temperature carries out mixing 3-5 minutes, then carry out cold mixed 2-5 at 60-80 DEG C
Prepared by being taken out after minute.
5. a kind of graphene Reinforced PVC composite pipe according to claim 1, it is characterised in that：The modified graphite
Alkene includes：The graphene that parts by weight are 10-20 parts is added in the batch mixer of 5-10L, then adds 1-5 parts of six methylenes
Group diisocyanate or polyisocyanic acid polymethylene polyphenyl ester, 1-2 parts of organotin, 3-5 parts of peroxide ethylene waxes, control are anti-
Answering kettle temperature degree, rotating speed 120-300 turns at 60-80 DEG C, and after then carrying out reaction 1-1.5 hours, temperature of reaction kettle is increased 2-5 DEG C
Afterwards, it adds in 1-2 parts of dibenzoyl peroxide then to carry out after reacting 1-2 hours, then take out after keeping the temperature 1 hour, obtain just
It is modified graphene.
6. graphene Reinforced PVC composite pipe according to claim 1, it is characterised in that：The filler material is activity
Calcium carbonate, one kind in activated silica diatomaceous earth, active high-level laterite, active coal ash.
7. a kind of graphene Reinforced PVC composite pipe according to claim 1, it is characterised in that：The antioxidant
By ordinary titanium powder, to add in baking oven and being dried, drying temperature adds in 100-200 DEG C, time 1-2 hour after drying
Enter in ball mill and be ground, granular size is taken out when being 500-100 mesh, and parts by weight then are calculated as 10-20 parts grinds
Titanium dioxide after mill is added in batch mixer, then add in 1-5 parts 2-hydroxy-4-n-octoxybenzophenone, 2-3 parts of 2-
Then (2 '-hydroxyl -3 ', 5 '-two tertiary phenyl) -5- chlorinations benzotriazole, 3-5 parts of peroxide ethylene waxes control temperature in 50-
80 DEG C taken out after mixing 10-20 minutes, obtain antioxidant.
8. a kind of graphene Reinforced PVC composite pipe according to claim 1, it is characterised in that：The toughener packet
It includes：The rubber powder, 2-8 parts of high glue powder, 10-15 parts of ABS that mass fraction is calculated as 20-50 parts are mixed, and what is obtained is mixed
Close object.
9. graphene Reinforced PVC composite pipe according to claim 1, it is characterised in that：The plasticizing accelerating agent is,
Parts by weight are calculated as 2-5 parts of polymethyl methacrylate, 3-4 parts of polyethyl methacrylate, 5-6 parts of polyacrylic acid
Ester, 3-6 parts of styrene is mixed, obtained mixture.
10. a kind of preparation method of graphene Reinforced PVC composite pipe as described in claim 1-10, it is characterised in that：Packet
Include following steps：
(1) mixing of raw material
It by PVC, stabilizer, in-lubricant, external lubricant, filler material, adds in batch mixer and is mixed by above-mentioned mass ratio, control
Batch mixer temperature processed carries out mixed on low speed 1-2 minutes first at 60-80 DEG C, is then turned on height and mixes, batch mixing presses matter after 5-10 minutes
Antioxidant, toughener, plasticizing accelerating agent, modified graphene are added in batch mixer than successively and carry out mixing 1-3 minutes by amount, will
Material is put into cold mixer and is mixed, and mixing is taken out after 5-10 minutes, obtains PVC multiple tube mixtures；
(2) preparation of PVC multiple tubes
Uniformly mixed PVC multiple tubes mixed material is added in, heat fusing extrusion is carried out in double screw extruder, it is compound to obtain PVC
Pipe；Its continuous extrusion industrial condition such as following table：
(3) it packs.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637273A (en) * | 2021-08-31 | 2021-11-12 | 浙江同正管道技术有限公司 | Graphene reinforced PVC pipe and preparation method thereof |
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| CN107245209A (en) * | 2017-08-03 | 2017-10-13 | 安徽真信涂料有限公司 | A kind of enhanced type PVC decorative material |
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| CN106519497A (en) * | 2016-11-06 | 2017-03-22 | 威海永利坚装饰有限公司 | Novel PVC (Polyvinyl Chloride) decorative material |
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Application publication date: 20180629 |