CN104877251B - A kind of environmentally friendly low cigarette leadless polyvinyl chloride electrician pipe and preparation method thereof - Google Patents
A kind of environmentally friendly low cigarette leadless polyvinyl chloride electrician pipe and preparation method thereof Download PDFInfo
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- CN104877251B CN104877251B CN201510149507.8A CN201510149507A CN104877251B CN 104877251 B CN104877251 B CN 104877251B CN 201510149507 A CN201510149507 A CN 201510149507A CN 104877251 B CN104877251 B CN 104877251B
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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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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
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- C08L2203/20—Applications use in electrical or conductive gadgets
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Abstract
The invention discloses environmentally friendly low cigarette leadless polyvinyl chloride electrician pipe of one kind and preparation method thereof, electricity Gong Guan is made up in terms of quality point of following component：100 parts of Corvic；20~25 parts of calcium carbonate；3.0~5.0 parts of organic composite heat stabilizer；8~12 parts of anti-impact agent；2~3 parts of hydrotalcite；5~8 parts of reinforcing agent；Without 2~4 parts of halogen smoke suppressing fire-retardant agent；1~2 part of inside and outside lubricant agent；TiO20.7~1.3 part.By recipe ratio, calcium carbonate mixed at high speed, the moisture in calcium carbonate of going out first are added；Add 2~3min of Corvic mixed at high speed；Add other components speed heat kneading high to close 10~15min afterwards, its temperature is reached 120~130 DEG C；Then again with the mixing speed of 10~15r/min when being cooled to 40~50 DEG C in the case of logical cooling water blowing；Finally it is heated to 150~220 DEG C of plasticating extrusions.The rigidity of electrician's pipe of the present invention is good, anti-bending strength is good, heat resistance and ageing-resistant performance is excellent, good insulating, and low cost of manufacture, processing technology is simple.
Description
Technical field
The present invention relates to polyvinyl chloride electrician's tube material field, and in particular to a kind of environmentally friendly low cigarette leadless polyvinyl chloride electrician
Pipe and preparation method.
Background technology
Polyvinyl chloride (PVC) is one of big resins for universal use (PE, PVC, PP, PS, ABS) of the world five, is to realize work in the world
The universal thermoplastic that the industry time is earliest, range of application is most wide.But PVC structural instabilities, hold in machine-shaping
It is degradable, when processing temperature reaches 90 DEG C, that is, there are slight pyrolysis；When temperature reaches 120 DEG C, that is, occur bright
Aobvious pyrolysis, make PVC colors gradually deepen.It is necessary to use heat stabilizer, PVC is prevented in process
Thermal decomposition.
Conventional heat stabilizer mainly has the stabilizers such as lead salts, metal soap, organic tin, terres rares and calcium zinc class.
With further enhancing for people's environmental consciousness, the usage amount of lead salt stabilizer is just gradually decreased.And organic tin is thermally-stabilised
Agent still cannot be promoted widely at present due to its price reasons.Nontoxic calcium zinc heat stabilizer is nothing generally acknowledged in the world at present
Poison, environment-benign heat stabilizer, and have the advantages that cheap, lubricity is good, therefore with extremely wide development space.And
With going deep into that national economy is reformed, the reinforcement of environmental protection consciousness so that the production of PVC product, the friendly chemical conversion of use environment
It is inexorable trend.
Electrician's pipe be it is a kind of it is electric install electric wire hard PVC sebific duct, it is necessary to meet anticorrosion, it is anticreep, fire-retardant and
The requirement such as good mechanical property.Existing electrician's tube material it is fire-retardant be divided into have that halogen is fire-retardant and halogen-free flameproof two types, its
In have that although the fire-retardant addition of halogen is small, fire resistance is high, can volatilize substantial amounts of toxic gas and dense smoke during its burning, cause
" secondary disaster ".The matrix of bittern-free flame-proof material is usually metal oxide, metallo-organic compound, water and metal hydroxides
Deng fire retardant is oxide of magnesium hydroxide, aluminium hydroxide, antimony trioxide, molybdenum etc..During such as single this based flame retardant of use, resistance
Fuel efficiency fruit is not ideal, and addition is larger, the cost for not only increasing product and the bending performance that have impact on material.
Also, production PVC electrician pipe largely uses lead salt stabilizer at present, and not only production process may be made to the producer
Into greatly injury and to surrounding enviroment, including water, soil and air, heavy metal deposition is caused, so as to living in this ring
The mankind and animal cause immeasurable healthy hidden danger in border.
Although traditional Ca/Zn composite thermal stabilizers make use of certain cooperative effect that both have, and become in recent years
Carry out most active research field in compound stabilizer, such as Liu Di is strong et al. Publication No. CN 101967253A middle promulgated by the State Council
A kind of environment-friendly PVC calcium zinc stabilizer is disclosed in bright Patent Application Publication, is related to the compounding of calcium stearate zinc salt, Li Jian, Wang Yang
It is thermally-stabilised that woods et al. discloses a kind of Ca Zn composite in the Chinese invention patent application document of Publication No. CN 101942110A
Agent, is related to the formula of calcium stearate zinc salt, Anhui Normal University Zhou Yunyou et al. in the China of Publication No. CN 102504340A
A kind of nontoxic calcium zinc heat stabilizer is disclosed in application for a patent for invention document, the side for being related to calcium zinc stabilizer molecular level to mix
Method, instead of traditional poisonous stabilizer well.
Therefore in sum, urgent need wants the good electrical casing pipe of a kind of unleaded, low cigarette, low halogen, fire resistance.
The content of the invention
The present invention provides a kind of environmentally friendly low cigarette leadless polyvinyl chloride electrician pipe and preparation method thereof, the rigidity of electrician's pipe
Good, good anti-bending strength, heat resistance and ageing-resistant performance is excellent, good insulating, low cost of manufacture, processing technology is simple.
A kind of environmentally friendly low cigarette leadless polyvinyl chloride electrician pipe, is made up in terms of quality point of following component：
Most preferably, it is made up of following component in terms of quality point：
Preferably, the organic composite heat stabilizer is by weight percentage, it is made up of following component：
Wherein, the uracil derivative base zinc salt is N, N- dimethyl -6- amino-uracils zinc salt, N- methyl -6- ammonia
Base Uracil zinc salt, one kind of N- methyl -6- aminothiouracils zinc salt and N, N- dimethyl -6- aminothiouracil zinc salts or
Several mixtures.
Preferably, by weight percentage, it is made up of following component：
Preferably, the diketone is 1, hydroresorcinol, 1- heptadecyl -3- phenylpropanediones, diphenylthanedione, hard
Acyl benzoyl methane, 4- p-methoxyphenyl -2, the mixture of one or more of 4- dioxobutyric acids.
Further preferably, the diketone is 1, hydroresorcinol, 17 alkyl -3- phenylpropanediones and diphenylthanedione
Mixture, wherein 1, the mol ratio of hydroresorcinol, 17 alkyl -3- phenylpropanediones and diphenylthanedione is 2：1：1.
Or：The diketone is mixed for hydroresorcinol, 17 alkyl -3- phenylpropanediones and stearoyl benzoyl methane
Compound, wherein 1, the mol ratio of the mixture of hydroresorcinol, 17 alkyl -3- phenylpropanediones and stearoyl benzoyl methane is
2:1:1。
Hydrotalcite uses epoxide as modifying agent, after epoxide is uniformly mixed with hydrotalcite, at 120 DEG C
Under temperature conditionss, clipped mixing is solidified into densified powder shape thing, is made epoxidation organic hydrotalcite.
Preferably, the organic hydrotalcite by weight percentage, consisting of：
Hydrotalcite-based compound 60~95%；
Epoxide 5~40%；
It is further preferred that the organic hydrotalcite is by weight percentage, consisting of：
Hydrotalcite-based compound 95%；
Epoxide 5%；
Wherein, the laminate cation of the hydrotalcite-based compound is Mg2+Or Al3+, interlayer anion is CO3 2-、OH-、
SO4 2-、NO3 -Or Cl-, the primary particle size of the hydrotalcite-based compound is 10~150nm；
The epoxide is bisphenol A epoxide resin, epoxy novolac resins, brominated bisphenol A epoxy resin or third
Olefin(e) acid bisphenol A epoxide resin.
The preparation method of the organic hydrotalcite is as follows：
Hydrotalcite-based compound and epoxide are mixed, at a temperature of 120 DEG C~160 DEG C, clipped mixing, solidification
Into closely knit powder, organic nano hydrotalcite is obtained.
Epoxidation organic hydrotalcite high temperature resistant and color-changing performance is good, and interlamellar spacing is big, reachable 1.11~3.0nm, in the polymer
Easily peelable dispersion.
Preferably, the multi-hydroxy stearic acid salt is hard lithium 12-hydroxy stearate, octohydroxy-stearic acid calcium, ten dihydroxy
Resin acid zinc, ten dihydroxystearic acid magnesium, the mixture of one or more of octohydroxy-stearic acid magnesium.
It is further preferred that by weight percentage, being made up of following component：
On the basis of recipe ratio is combinations thereof, the component is selected from following combination：
N, N- dimethyl -6- amino-uracils zinc salt, organic nano hydrotalcite, lithium 12-hydroxy stearate and 1,3- hexamethylene
Diketone.
Or：
N- methyl -6- amino-uracils zinc salt, organic nano hydrotalcite, two alcohol/ketone mixtures and octohydroxy-stearic acid magnesium；Its
In two alcohol/ketone mixtures be mol ratio be 2:1:1 hydroresorcinol, 17 alkyl -3- phenylpropanediones and diphenylthanedione
Mixture.
Or：
N- methyl -6- thiosemicarbazides zinc salt, organic nano hydrotalcite, two alcohol/ketone mixtures and lithium 12-hydroxy stearate；Its
In two alcohol/ketone mixtures be mol ratio be 2:1:1 hydroresorcinol, 17 alkyl -3- phenylpropanediones and stearoyl benzoyl first
The mixture of alkane
Or：
N, N- dimethyl -6- thiosemicarbazides zinc salt, organic nano hydrotalcite, two alcohol/ketone mixtures and octohydroxy-stearic acid calcium；
Wherein two alcohol/ketone mixtures are that mol ratio is 2:1:1 hydroresorcinol, 17 alkyl -3- phenylpropanediones and diphenylthanedione
Mixture.
Most preferably, the organic composite heat stabilizer is that mass ratio is 0.6:0.20.05:0.12 N, N- dimethyl-
6- thiosemicarbazides zinc salt, organic nano hydrotalcite, two alcohol/ketone mixtures and octohydroxy-stearic acid calcium；Wherein two alcohol/ketone mixtures for mole
Than being 2:1:The mixture of 1 hydroresorcinol, 17 alkyl -3- phenylpropanediones and diphenylthanedione.
Organic composite heat stabilizer is preferably adopted and prepared with the following method：
By recipe ratio by uracil derivative base zinc salt, diketone, organic hydrotalcite and multi-hydroxy stearic acid salt 60~85
DEG C carry out mixed at high speed, then feed the mixture into single screw extrusion machine, extrusion is bonded at 60~80 DEG C, cooled down by air
Master batch of the pelletizing into 2~3mm afterwards.
Preferably, the N, N- dimethyl -6- amino-uracil zinc salt preparation methods are as follows：
0.1mol metallic sodiums will be added in 100ml absolute ethyl alcohols, prepared dense caustic alcohol/ethanol is molten after being stirred at reflux 0.5h
Liquid；0.1mol urea, 0.2mol cyanoacetic acids, 0.1mol acetic anhydrides react backflow 40min in the 500ml there-necked flasks at 80 DEG C
Afterwards, add obtained dense caustic alcohol/ethanol solution 100ml to continue to be heated to reflux 3h, then be slowly added dropwise hydrochloric acid solution pH and be adjusted to 7,
It is subsequently adding stearic acid 0.1mol and melts dissolving completely to it；After temperature is risen into 95 DEG C, 0.1mol zinc chloride are slowly added dropwise, dripped
2.5h is stirred for after complete, after being cooled to room temperature, by product suction filtration, is infiltrated with water smoke and washed, in 80~90 DEG C of drying to constant weight, system
It is standby to obtain N, N- dimethyl -6- amino-uracil zinc salts.
N- methyl -6- amino-uracil zinc salt the preparation methods are as follows：
0.1mol metallic sodiums will be added in 100ml absolute ethyl alcohols, prepared dense caustic alcohol/ethanol is molten after being stirred at reflux 0.5h
Liquid；After adding 0.1mol urea continuation backflow 0.5h, dropwise addition 10.6ml ethyl cyanoacetates continue to flow back after 3h is cooled down and slowly drip again
Plus hydrochloric acid solution PH is adjusted to 7, it is subsequently adding stearic acid 0.1mol and melts dissolving completely to it；After temperature is risen into 90~95 DEG C,
0.1mol zinc chloride are slowly added dropwise, 2.5h are stirred for after dripping off, after being cooled to room temperature, by product suction filtration, infiltrated with water smoke and washed,
In 80~90 DEG C of drying to constant weight, N- methyl -6- amino-uracil zinc salts are prepared.
N- methyl -6- thiosemicarbazides zinc salt the preparation methods are as follows：
0.1mol metallic sodiums will be added in 100ml absolute ethyl alcohols, prepared dense caustic alcohol/ethanol is molten after being stirred at reflux 0.5h
Liquid, after being subsequently adding 0.1mol thiocarbamides continuation backflow 0.5h, the ethyl cyanoacetate that 10.6ml is added dropwise continues the 3h that flows back.Dripped after cooling
Plus 4mol/L hydrochloric acid solutions adjust PH to 7, are subsequently adding stearic acid 0.1mol and melt dissolving completely to it；Temperature is risen to 90~
After 95 DEG C, 0.1mol Zinc vitriols are slowly added dropwise, 2.5h is stirred for after dripping off, after being cooled to room temperature, product suction filtration used
Water smoke infiltration washing, in 80~90 DEG C of drying to constant weight, prepares N- methyl -6- thiosemicarbazides zinc salts.
The N, N- dimethyl -6- thiosemicarbazides zinc salt preparation methods are as follows：
0.1mol metallic sodiums will be added in 100ml absolute ethyl alcohols, prepared dense caustic alcohol/ethanol is molten after being stirred at reflux 0.5h
Liquid；0.1mol thiocarbamides, 0.2mol cyanoacetic acids, 0.1mol acetic anhydrides react backflow 40min in the 500ml there-necked flasks at 80 DEG C
Afterwards, add obtained dense caustic alcohol/ethanol solution 100ml to continue to be heated to reflux 3h, then be slowly added dropwise hydrochloric acid solution pH and be adjusted to 7,
It is subsequently adding stearic acid 0.1mol and melts dissolving completely to it；After temperature is risen into 95 DEG C, 0.1mol zinc chloride are slowly added dropwise, dripped
2.5h is stirred for after complete, after being cooled to room temperature, by product suction filtration, is infiltrated with water smoke and washed, in 80~90 DEG C of drying to constant weight, system
It is standby to obtain N, N- dimethyl -6- thiosemicarbazides zinc salts.
Preferably, described without halogen smoke suppressing fire-retardant agent mass ratio 1:3:20 antimony oxide and molybdenum trioxide and antismoke agent
Mixture.The antismoke agent is this area routine smoke of gunpowder agent, such as Firebrake ZB.
The inside and outside lubricant agent is that mass ratio is 12:1:1:2 polyethylene (PE) wax, calcium stearate, stearic acid and single sweet
The mixture of ester；Reinforcing agent is nano-calcium carbonate that particle diameter is 0.01~0.05 μm；Anti-impact agent is ACM.
The organic composite heat stabilizer that the present invention is used contains following material：Uracil derivative base zinc salt, polyhydroxy are hard
Resin acid salt, diketone and organic hydrotalcite.The present invention use heat stabilizer compared with existing heat stabilizer, using one pot process
Uracil derivative base zinc salt is generated with zinc salt chemical mixing after uracil derivative, more current physical mixed calcium zinc is thermally-stabilised
Agent, directly substitute existing calcium salt using the more preferably more efficient uracil derivative that acts synergistically carries out being mixed on molecular level with zinc salt
Close, the polysubstituted uracil of another anion is introduced again on the basis of a kind of anion is stearic, urinate phonetic using polysubstituted amino
The characteristic of piperidine derivatives, then it is aided with organic hydrotalcite, two alcohol/ketone mixtures and multi-hydroxy stearic acid salt, stabilizer is delayed significantly
" zinc burning " phenomenon.Wherein, organic hydrotalcite has good association after epoxy compound finishing with uracil derivative base zinc salt
Same-action, thermal stability obtains the lifting of matter, and weatherability is strong, the transparency, and the processing characteristics such as compatibility there has also been larger carrying
Height, without any toxic component in mixture, it is nontoxic to be truly realized high-efficiency environment friendly, then is extruded by low temperature and be made master batch, and energy
The dust that produces when reducing production dispensing, made heat stabilizer have excellent static heat stability, dynamic thermally-stabilised new and
Hold color.
It is as follows that the present invention also provides a kind of preparation method of low cigarette leadless polyvinyl chloride electrician's pipe environmentally friendly as described, including such as
Lower step：
By recipe ratio, calcium carbonate mixed at high speed is first added, remove the moisture in calcium carbonate；Add Corvic high
2~3min of speed mixing；Add other components speed heat kneading high to close 10~15min afterwards, its temperature is reached 120~130 DEG C；So
Afterwards again with the mixing speed of 10~15r/min when being cooled to 40~50 DEG C in the case of logical cooling water blowing；Finally reheat
To 150~220 DEG C of plasticating extrusions.
Most preferably, calcium carbonate mixed at high speed is first added, the moisture in calcium carbonate is removed；Add Corvic high
Speed mixing 3min；Add other components speed heat kneading high to close 13min afterwards, its temperature is reached 125 DEG C；Then again with 13r/
The mixing speed of min blowing when being cooled to 50 DEG C in the case of logical cooling water；190 DEG C of plasticizings are finally heated to be extruded into
Type.
Compared with prior art, the present invention has the advantages that：
The heat stabilizer that the present invention is used combines the respective performance characteristics of polysubstituted amino-uracil and stearate radical, with reference to
Uracil derivative and the shot and long term stability feature of zinc soap, the mixing of its molecular level is realized with one kettle way, and product is mixed
Uniform, good dispersion is closed, simple and easy to operate, yield is high.It is aided with obtained with hydrotalcite-based compound and epoxide mixing
Organic hydrotalcite and various diketone, are obtained master batch so that the heat stabilizer system performance is remarkable, breaks by low temperature adhesion extrusion
Traditional simple Ca/Zn stearate compounds the constraint of theory, solve that its performance is single, " zinc burnings " phenomenon it is still substantially etc. scarce
Point, as the characteristics of every kind of material can play respective in molecule rank, coefficient non-toxic organic composite highly effective heat it is steady
Determine agent.
The electrician manufactured using the environmentally friendly low cigarette leadless polyvinyl chloride electrician tube material of composite thermal stabilizer of the present invention is managed, phase
Than in it is present it is leaded there is the fire-retardant electrician of halogen to manage, its fire resistance is good, and due to being free of halogen in fire retardant, exhaust gas volumn is small, toxicity
It is low；As a result of environmentally friendly calcium zinc heat stabilizer so that the production process of this electrician's pipe is small to the body harm of workman, production and
Using process to more environment-friendly.
Electrician's pipe of the invention complies fully with electrical casing pipe industry quality standard JG3050-1998 for building, and fire-retardant effect
Really good, due to being free of halogen in fire retardant, therefore smoke amount is small, and smoke amount is than common electrical pipe reduction by 50%~60%；Not only
In this way, because used Environment-friendlyheat heat stabilizer, its toxotest has reached European Union's ROSH standards so that the production of product and use
Process is more environment-friendly.Below below 2000V and continuous 90 DEG C of operating temperature suitable for industry and architectural engineering
Electric wire is protected.The rigidity of electrician's pipe is good, anti-bending strength is good, heat resistance and ageing-resistant performance is excellent, good insulating, manufacture
Low cost, processing technology is simple.
Specific embodiment
It is raw materials used in following examples to be commercial goods.
Embodiment 1
0.1mol metallic sodiums will be added in 100ml absolute ethyl alcohols, prepared dense caustic alcohol/ethanol is molten after being stirred at reflux 0.5h
Liquid；0.1mol urea, 0.2mol cyanoacetic acids, 0.1mol acetic anhydrides react backflow 40min in the 500ml there-necked flasks at 80 DEG C
Afterwards, add obtained dense caustic alcohol/ethanol solution 100ml to continue to be heated to reflux 3h, then be slowly added dropwise hydrochloric acid solution pH and be adjusted to 7,
It is subsequently adding stearic acid 0.1mol and melts dissolving completely to it；After temperature is risen into 95 DEG C, 0.1mol zinc chloride are slowly added dropwise, dripped
2.5h is stirred for after complete, after being cooled to room temperature, by product suction filtration, is infiltrated with water smoke and washed, in 80~90 DEG C of drying to constant weight, system
It is standby to obtain N, N- dimethyl -6- amino-uracil zinc salts, yield 83%.
It is CO by anion3 2-Hydrotalcite 0.95kg, epoxide number is 0.4~0.6 bisphenol A epoxide resin (E44)
0.05kg, after premixing is uniform, on 142 DEG C of kneading machine, shearing mixing 20min obtains closely knit powder, then size-reduced mistake
Sieve, is obtained organic nano hydrotalcite.
By N, N- dimethyl -6- amino-uracil zinc salts 0.5kg, organic nano hydrotalcite 0.4kg, ten dihydroxystearic acids
Lithium 0.1kg and 1, hydroresorcinol 0.1kg carry out 70 DEG C of mixing, then feed the mixture into banburying single screw extrusion machine (GLD-
150) in, extrusion is bonded at 60~85 DEG C, into the master batch of 2~3mm, organic composite is prepared by pelletizing after air cooling
Heat stabilizer.
Embodiment 2
0.1mol metallic sodiums will be added in 100ml absolute ethyl alcohols, prepared dense caustic alcohol/ethanol is molten after being stirred at reflux 0.5h
Liquid；After adding 0.1mol urea continuation backflow 0.5h, dropwise addition 10.6ml ethyl cyanoacetates continue to flow back after 3h is cooled down and slowly drip again
Plus hydrochloric acid solution PH is adjusted to 7, it is subsequently adding stearic acid 0.1mol and melts dissolving completely to it；After temperature is risen into 90~95 DEG C,
0.1mol zinc chloride are slowly added dropwise, 2.5h are stirred for after dripping off, after being cooled to room temperature, by product suction filtration, infiltrated with water smoke and washed,
In 80~90 DEG C of drying to constant weight, N- methyl -6- amino-uracil zinc salts, yield 93% are prepared.
It is CO by anion3 2-Hydrotalcite 0.95kg, epoxide number is 0.4~0.6 bisphenol A epoxide resin (E44)
0.05kg, after premixing is uniform, on 135 DEG C of kneading machine, shearing mixing 20min obtains closely knit powder, then size-reduced mistake
Sieve, is obtained organic nano hydrotalcite.
0.2mol1,3- cyclohexanediones, 0.1mol1-17 alkyl -3- phenylpropanediones, 0.1mol diphenylthanediones are existed
It is well mixed at 70 DEG C in 1000ml beakers, cooling room temperature obtains two alcohol/ketone mixtures.
By N- methyl -6- amino-uracil zinc salts 0.5kg, organic nano hydrotalcite 0.4kg, two alcohol/ketone mixtures 0.1kg and
Octohydroxy-stearic acid magnesium 0.1kg carries out 70 DEG C of mixed at high speed, then feeds the mixture into banburying single screw extrusion machine, 60~85
Extrusion is bonded at DEG C, into the master batch of 2~3mm, organic composite heat stabilizer is prepared by pelletizing after air cooling.
Embodiment 3
0.1mol metallic sodiums will be added in 100ml absolute ethyl alcohols, prepared dense caustic alcohol/ethanol is molten after being stirred at reflux 0.5h
Liquid, after being subsequently adding 0.1mol thiocarbamides continuation backflow 0.5h, the ethyl cyanoacetate that 10.6ml is added dropwise continues the 3h that flows back.Dripped after cooling
Plus 4mol/L hydrochloric acid solutions adjust PH to 7, are subsequently adding stearic acid 0.1mol and melt dissolving completely to it；Temperature is risen to 90~
After 95 DEG C, 0.1mol Zinc vitriols are slowly added dropwise, 2.5h is stirred for after dripping off, after being cooled to room temperature, product suction filtration used
Water smoke infiltration washing, in 80~90 DEG C of drying to constant weight, prepares N- methyl -6- thiosemicarbazides zinc salts, yield 95%.
It is CO by anion3 2-Hydrotalcite 0.95kg, epoxide number is 0.4~0.6 bisphenol A epoxide resin (E44)
0.05kg, after premixing is uniform, on 140 DEG C of kneading machine, shearing mixing 20min obtains closely knit powder, then size-reduced mistake
Sieve, is obtained organic nano hydrotalcite.
By 0.2mol1,3- cyclohexanediones, 0.1mol1-17 alkyl -3- phenylpropanediones, 0.1mol stearoyl benzoyl first
Alkane is well mixed in the 1000ml beakers at 70 DEG C, and cooling room temperature obtains two alcohol/ketone mixtures.
By N- methyl -6- thiosemicarbazides zinc salts 0.55kg, organic nano hydrotalcite 0.38kg, two alcohol/ketone mixtures 0.08kg and
Lithium 12-hydroxy stearate 0.07kg carries out 70 DEG C of mixed at high speed, then feeds the mixture into single screw extrusion machine, 60~80
Extrusion is bonded at DEG C, into the master batch of 2~3mm, organic composite heat stabilizer is prepared by pelletizing after air cooling.
Embodiment 4
0.1mol metallic sodiums will be added in 100ml absolute ethyl alcohols, prepared dense caustic alcohol/ethanol is molten after being stirred at reflux 0.5h
Liquid；0.1mol thiocarbamides, 0.2mol cyanoacetic acids, 0.1mol acetic anhydrides react backflow 40min in the 500ml there-necked flasks at 80 DEG C
Afterwards, add obtained dense caustic alcohol/ethanol solution 100ml to continue to be heated to reflux 3h, then be slowly added dropwise hydrochloric acid solution pH and be adjusted to 7,
It is subsequently adding stearic acid 0.1mol and melts dissolving completely to it；After temperature is risen into 95 DEG C, 0.1mol zinc chloride are slowly added dropwise, dripped
2.5h is stirred for after complete, after being cooled to room temperature, by product suction filtration, is infiltrated with water smoke and washed, in 80~90 DEG C of drying to constant weight, system
It is standby to obtain N, N- dimethyl -6- thiosemicarbazides zinc salts, yield 81%.
It is NO by anion3 -Hydrotalcite 0.65kg, methacrylic acid bisphenol A epoxide resin (V118) 0.35kg, premix
After closing uniformly, on 140 DEG C of kneading machine, shearing mixing 20min obtains closely knit powder, then size-reduced sieving, is organic water
Talcum.
0.2mol1,3- cyclohexanediones, 0.1mol1-17 alkyl -3- phenylpropanediones, 0.1mol diphenylthanediones are existed
It is well mixed at 70 DEG C in 1000ml beakers, cooling room temperature obtains two alcohol/ketone mixtures.
By N, N- dimethyl -6- thiosemicarbazides zinc salts 0.6kg, organic nano hydrotalcite 0.20kg, two alcohol/ketone mixtures
0.05kg and octohydroxy-stearic acid calcium 0.12kg carry out 70 DEG C of mixed at high speed, then feed the mixture into single screw extrusion machine,
Extrusion is bonded at 60~80 DEG C, into the master batch of 2~3mm, organic composite heat stabilizer is prepared by pelletizing after air cooling.
Embodiment 5~9
Recipe ratio (mass ratio) as shown in table 1, first adds calcium carbonate mixed at high speed, the moisture in calcium carbonate of going out；Again plus
Enter 2~3min of Corvic mixed at high speed；Add other components speed heat kneading high to close 10~15min afterwards, make its temperature
Reach 120~130 DEG C；Then 40~50 DEG C are cooled in the case of logical cooling water with the mixing speed of 10~15r/min again
When blowing；Finally it is heated to 150~220 DEG C of plasticating extrusions.
The component of table 1 and content table
Wherein：The organic composite heat stabilizer used in embodiment 5 is prepared for embodiment 1, and what is used in embodiment 6 is organic
Composite thermal stabilizer is prepared for embodiment 2, and the organic composite heat stabilizer used in embodiment 7 is prepared for embodiment 3, embodiment
The organic composite heat stabilizer used in 8 and 9 is prepared for embodiment 4.
Organic nano hydrotalcite in embodiment 5~9 is prepared as：It is NO by anion3 -Hydrotalcite 0.65kg, methyl-prop
Olefin(e) acid bisphenol A epoxide resin (V118) 0.35kg, after premixing is uniform, on 140 DEG C of kneading machine, shearing mixing 20min is obtained
It is organic hydrotalcite to closely knit powder, then size-reduced sieving.
Lubricant is that mass ratio is 12:1:1:The mixture of 2 PE waxes, calcium stearate, stearic acid and monoglyceride；Reinforcing agent
It is the nano-calcium carbonate that particle diameter is 0.01~0.05 μm；Anti-impact agent is ACM.It is mass ratio 1 without halogen smoke suppressing fire-retardant agent:3:The three of 20
Aoxidize two antimony and molybdenum trioxide and smoke elimination agent composition.Calcium carbonate, anti-impact agent ACM, hydrotalcite, reinforcing agent, lubricant and TiO2
It is commercial sources common in electrician's pipe industry.
Below by taking the component of embodiment in table 9 as an example, the environmentally friendly low cigarette leadless polyvinyl chloride electrician pipe of the present invention is described in detail
The manufacture method of material：
First by 100 parts of component raw material Corvic, 25 parts of calcium carbonate, 3.8 parts of organic composite heat stabilizer, anti-impact
Agent ACM8 parts, 3 parts of hydrotalcite, 5 parts of reinforcing agent, without 3 parts of halogen smoke suppressing fire-retardant agent, 2 parts of inside and outside lubricant agent, TiO20.9 part is got ready, is pressed
Following steps are carried out：First add calcium carbonate mixed at high speed, the moisture in calcium carbonate of going out；Add Corvic mixed at a high speed
Close 3min；Add other components speed heat kneading high to close 13min afterwards, its temperature is reached 125 DEG C；Then again with 13r/min's
Mixing speed blowing when being cooled to 50 DEG C in the case of logical cooling water；Finally it is heated to 190 DEG C of plasticating extrusions.Implement
The performance test results of example 5~9 are as shown in the table：
The performance test table of comparisons of table 2
According to actual test, Corvic can 2~3min of mixed at high speed；Speed heat kneading high is closed mixing time and can be controlled
, in 10~15min, temperature control is at 120~130 DEG C for system；Mixing speed can be controlled in 10~15r/min, in logical cooling water
In the case of when being cooled to 40~50 DEG C by blowing；Last heating and temperature control is that plasticization is extruded at 150~220 DEG C
Type.
The electrician produced using above-mentioned preferred ingredient and method is managed, and complies fully with electrical casing pipe industry quality standard for building
JG3050-1998, and good flame retardation effect, due to being free of halogen in fire retardant, therefore smoke amount is small, and smoke amount is than common electrical pipe
50%~60% is reduced, oxygen index (OI) OI >=50 meet the requirement of public security GA305 standards；Moreover, because having used environment protection thermal steady
Determine agent, detect that its toxotest has reached European Union's RoSH2.0 standards through SGS so that the production of product and use process are more
It is environment-friendly.The electric wire below below 2000V and continuous 90 DEG C of operating temperature suitable for industry and architectural engineering is protected
Shield.The rigidity of electrician's pipe is good, anti-bending strength is good, heat resistance and ageing-resistant performance is excellent, good insulating, low cost of manufacture, plus
Work process is simple.
Above-described is only part preferred embodiment of the invention, it is noted that for a person skilled in the art,
On the premise of instant component and manufacture method is not departed from, some improvement can also be made, these should also be considered as the present invention
Protection domain.
Claims (5)
1. a kind of environmentally friendly low cigarette leadless polyvinyl chloride electrician manages, it is characterised in that be made up of following component in terms of mass parts：
The organic composite heat stabilizer by weight percentage, is made up of following component：
The uracil derivative base zinc salt is N- methyl -6- amino-uracils zinc salt, N- methyl -6- aminothiouracil zinc salts
And the mixture of one or more of N, N- dimethyl -6- aminothiouracil zinc salts；
The organic hydrotalcite by weight percentage, consisting of：
Hydrotalcite-based compound 60~95%；
Epoxide 5~40%；
Wherein, the laminate cation of the hydrotalcite-based compound is Mg2+Or Al3+, interlayer anion is CO3 2-、OH-、SO4 2-、
NO3 -Or Cl-, the primary particle size of the hydrotalcite-based compound is 10~150nm；
The epoxide is bisphenol A epoxide resin, epoxy novolac resins, brominated bisphenol A epoxy resin or acrylic acid
Bisphenol A epoxide resin；
The low cigarette leadless polyvinyl chloride electrician pipe of environmental protection is prepared by the method for comprising the following steps：
Calcium carbonate mixed at high speed is first added by recipe ratio, the moisture in calcium carbonate is removed；Add Corvic mixed at a high speed
Close 2~3min；Add other components speed heat kneading high to close 10~15min afterwards, its temperature is reached 120~130 DEG C；Then again
With the mixing speed of 10~15r/min when being cooled to 40~50 DEG C in the case of logical cooling water blowing；Finally it is heated to 150
~220 DEG C of plasticating extrusions.
2. environmentally friendly low cigarette leadless polyvinyl chloride electrician manages according to claim 1, it is characterised in that the diketone is 1,3- rings
Acetyl butyryl, 1- heptadecyl -3- phenylpropanediones, diphenylthanedione, stearoyl benzoyl methane, 4- p-methoxyphenyls -
The mixture of one or more of 2,4- dioxobutyric acids.
3. environmentally friendly low cigarette leadless polyvinyl chloride electrician manages according to claim 1, it is characterised in that the multi-hydroxy stearic acid
Salt is lithium 12-hydroxy stearate, octohydroxy-stearic acid calcium, ten dihydroxystearic acid zinc, ten dihydroxystearic acid magnesium, eight hydroxyls
The mixture of one or more of magnesium stearate.
4. environmentally friendly low cigarette leadless polyvinyl chloride electrician manages according to claim 1, it is characterised in that described without halogen smoke suppressing fire-retardant
Agent is that mass ratio is 1:3:The mixture of 20 antimony oxide, molybdenum trioxide and antismoke agent.
5. environmentally friendly low cigarette leadless polyvinyl chloride electrician pipe according to claim 1, it is characterised in that the inside and outside lubricant agent is
Mass ratio is 12:1:1:The mixture of 2 Tissuemat E, calcium stearate, stearic acid and monoglyceride；Reinforcing agent is that particle diameter is 0.01
~0.05 μm of nano-calcium carbonate；Anti-impact agent is ACM.
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| CN106633469A (en) * | 2016-10-08 | 2017-05-10 | 深圳市志海实业股份有限公司 | Preparation and application of novel environment-friendly uracil zinc compound stabilizers for PVC (polyvinyl chloride) pipes |
| CN106432971A (en) * | 2016-10-09 | 2017-02-22 | 深圳市志海实业股份有限公司 | Preparation and application of novel environment-friendly foaming PVC specific uracil zinc composite stabilizer |
| CN107325435A (en) * | 2017-06-26 | 2017-11-07 | 周小红 | High-temperature resistant plastic pipes and preparation method thereof |
| CN110628146A (en) * | 2019-09-09 | 2019-12-31 | 浙江同正管道技术有限公司 | High-temperature-resistant transparent hard PVC electrical threading pipe and preparation method thereof |
| CN111286137B (en) * | 2020-04-09 | 2022-03-15 | 宁波尚瑞塑胶实业有限公司 | Modified PVC (polyvinyl chloride) particles and preparation method thereof |
| CN112143128B (en) * | 2020-09-03 | 2022-08-09 | 杭州鸿雁管道系统科技有限公司 | Visual PVC-U flame-retardant pipe groove and preparation method thereof |
| CN112321968B (en) * | 2020-11-11 | 2022-08-02 | 济南市阿波罗木塑复合材料有限公司 | PVC-bauxite curb stone and preparation method thereof |
| CN113402826B (en) * | 2021-07-05 | 2022-08-23 | 深圳市鹏塑科技发展有限公司 | Environment-friendly high-strength polyvinyl chloride cable material and preparation method thereof |
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| CN103183644A (en) * | 2011-12-31 | 2013-07-03 | 深圳市志海实业有限公司 | Uracil zinc salt and application thereof as heat stabilizer for PVC |
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| CN101671415B (en) * | 2008-09-11 | 2012-05-23 | 杭州三叶新材料股份有限公司 | Method for preparing soft PVC special for cable wires |
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| CN1515610A (en) * | 1995-10-13 | 2004-07-28 | ����ķ�ն���ϩ��Ӽ�����˾ | Stabilizing agent copmosition for chlorine-containing polymer |
| CN102120856A (en) * | 2011-01-13 | 2011-07-13 | 杭州鸿雁电器有限公司 | Polyvinyl chloride/organic hydrotalcite nanocomposite and preparation method thereof |
| CN103183644A (en) * | 2011-12-31 | 2013-07-03 | 深圳市志海实业有限公司 | Uracil zinc salt and application thereof as heat stabilizer for PVC |
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