CN105001561B - Flame retardant polyvinyl chloride composition and preparation method thereof - Google Patents
Flame retardant polyvinyl chloride composition and preparation method thereof Download PDFInfo
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- CN105001561B CN105001561B CN201510556432.5A CN201510556432A CN105001561B CN 105001561 B CN105001561 B CN 105001561B CN 201510556432 A CN201510556432 A CN 201510556432A CN 105001561 B CN105001561 B CN 105001561B
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides a flame retardant polyvinyl chloride composition and a preparation method thereof, which comprises the following components in parts by weight: 100 parts of polyvinyl chloride resin, 1 to 45 parts of plasticizer, 10 to 90 parts of superfine active magnesium calcium powder, 0 to 10 parts of zinc borate, 0 to 10 parts of antimonous oxide, 0 to 60 parts of magnesium hydroxide, 0 to 25 parts of epoxidized soybean oil, 0 to 70 parts of chlorinated paraffin, 0 to 8 parts of Ca-Zn composite stabilizer, 0 to 5 parts of zinc oxide, and 0 to 20 parts of phosphotriester. The flame retardant polyvinyl chloride composition and the preparation method thereof provided by the invention has the beneficial effects that the flame retardant polyvinyl chloride composition not only has good mechanical property, processability and high temperature resistance, but also has low halogen and high flame retardance; the cost is low, and the flame retardant polyvinyl chloride composition can be used for producing flame retardant wires and cables or other flame retardant products.
Description
Technical field
The present invention relates to a kind of fire retardant polychloroethylene composition and preparation method thereof, belongs to fire retardant high polymer material technology neck
Domain.
Background technology
Traditional cable typically using polrvinyl chloride as sheath, although pvc material have preferable cost performance,
The features such as expressing technique is good, but as which contains halogen, a large amount of hydrogen halides and dense smoke during burning, can be released, people once inhale
Easily produce after entering excessive toxic gas and be poisoned to death.Therefore, with the development and the continuous improvement of people's safety consciousness of society,
The performance of fire proofing material is put forward higher requirement.
The characteristics of low-smoke halogen-free cable is that not only have excellent fire resistance, and constitutes the material of low-smoke halogen-free cable
Not halogen-containing, the corrosivity and toxicity during burning are relatively low, produce minimal amount of smog, reduce to human body, instrument and equipment
Infringement, but its mechanically and electrically performance it is more slightly worse than common cable and expensive.
And low halogen flame retardant cable is typically with polrvinyl chloride (PVC) as base material, then be equipped with efficient flame-retarding agent, HCl absorbent and
Smoke suppressant is processed.This kind of fire proofing significantly improves the combustibility of common flame-proof polyvinyl chloride material, and not only price is low
It is honest and clean, with very high cost performance.
Additionally, the cost performance that plastics modified by inorganic powder has had, is one of important kind of environmentally friendly plastics.Due to
Inorganic particle can both reduce the cost of polymer-based composite, can improve the rigid of macromolecular material, hardness, dimensionally stable again
Property, or even give composite some special physical and chemical performances, such as：Corrosion resistance, flame retardancy etc., can comprehensively improve high score
The environment friendly of sub- material.Mainly there are Calcium Carbonate, aluminium hydroxide, magnesium hydroxide currently used for the fire retardant inorganic particle of compound
Deng.Such as partial cables material generally adopts modified calcium carbonate as inserts, but as the decomposition temperature of Calcium Carbonate is up to 900
DEG C, it is difficult to decompose release carbon dioxide in flame initial period, the performance of its fire retardant effect being affected, its flame retardant effect has
Limit；Hydroxide is heated release water outlet, and water becomes steam after being heated, and the heat of transformation is larger, absorbing material surface heat, the same to time-division
Oxide after solution is covered in the contact that material surface can be with blocking material with oxidant, can delay the burning of polymer, from
And fire retardant effect is played, therefore hydroxide is received much concern in recent years as fire retardant compound filler.
The content of the invention
The technical problem to be solved in the invention is to provide a kind of fire retardant polychloroethylene composition and preparation method, using this
Invention preparation method can be used to produce the fire retardant electric wire of low halogen.
To achieve these goals, technical scheme is as follows：
A kind of fire retardant polychloroethylene composition, which includes the following component counted by weight：
The preparation method of superfine active magnesium calcium powder therein refers to Chinese patent ZL200610135382.4.
Preferably, the parts by weight of each component are respectively：
Preferably, the plasticizer is diethylene glycol dibenzoate, epoxy aliphatic acid methyl ester, phthalic acid two
At least one in monooctyl ester, diphenyl 2 ethylhexyl phosphate, triaryl phosphate.
A kind of preparation method of fire retardant polychloroethylene composition as the aforementioned, which comprises the steps：
By in Corvic, superfine active magnesium calcium powder, plasticizer and incombustible agent, stabilizer, smoke suppressant at least
After a kind of auxiliary agent mixing, carry out double roller and plasticate；Tested after vulcanizer press-molding again, after product is up to standard, blanking.
Preferably, the temperature that the double roller is plasticated is 170～180 DEG C.
Preferably, the time that the double roller is plasticated is 8～10min.
Preferably, the temperature of the tabletting is 75～85 DEG C, and the time of tabletting is 4～6min.
Superfine active magnesium calcium powder (such as Fig. 1 XRD spectra) used by the present application is not only able to endothermic decomposition, and
Water outlet and carbon dioxide can also be discharged.Therefore, there are some at the fire retardant aspect of compound and potentially should in superfine active magnesium calcium powder
With.In the present application, by thermogravimetric (TG), differential thermal analyses (DTA), superfine active magnesium disguises end has multiple at 220～450 DEG C
Decomposition temperature, such as Fig. 2, can absorb heat, and that what is discharged is H2O and CO2, will not generation environment burden, belong to a kind of green
The free of contamination inorganic additive of color, is a kind of potential inorganic nonflammable material, is expected to as a kind of potential inorganic fire retardant filler
Substitute poisonous and expensive incombustible agent to apply in the industry for there are fire-retardant needs.
The beneficial effects are mainly as follows：The fire retardant polychloroethylene composition of the present invention can ensure that material except having
Good mechanical property, processing characteristics be outer and good resistance to elevated temperatures outside, also with extraordinary high flame retardant property, Er Qiecheng
This is low, can be used to produce fire retardant electric wire.
Description of the drawings
Detailed description non-limiting example made with reference to the following drawings by reading, the further feature of the present invention,
Objects and advantages will become more apparent upon：
Fig. 1 is superfine active magnesium calcium powder XRD spectra in the present invention；
Fig. 2 is superfine active magnesium calcium powder feature DTA-TG curve chart in the present invention；
Fig. 3 is cost after the model optimization drawn according to embodiment 8-22 in the present invention, DOP, PCl triadic relation figure；
Fig. 4 is cost after the model optimization drawn according to embodiment 23-35 in the present invention, DOP, PCl triadic relation figure.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, some deformations and improvement can also be made.These belong to the present invention
Protection domain.
Polyvinyl chloride resin, fire retardant system auxiliary agent and other commercial auxiliaries first pass through weighing batch mixing, then fill in high-speed mixer
Divide mixing, the material for mixing tabletting sizing to be carried out using vulcanizer Jing after double roller is plasticated again, finally take out sample and mark by related
Alignment request carries out performance test.
Embodiment 1
100 parts of polrvinyl chloride (PVC), 50 parts of superfine active magnesium calcium powder (hereinafter referred to as magnesium calcium powder), 12 parts of DOP, PCl
12 parts, 8 parts of ESO, 10 parts of TCEP, 6 parts of ZB, 8 parts of calcium zinc stabilizer.
Test result, oxygen index (OI) OI are 30.1, tensile strength 15.2MPa, elongation at break 170.6%.
Embodiment 2
100 parts of polrvinyl chloride, 20 parts of magnesium calcium powder, 3 parts of DOP, 6 parts of PCl, 10.5 parts of ESO, 16.5 parts of TCEP, ZB 14
Part, 8 parts of calcium zinc stabilizer.
Test result, oxygen index (OI) OI are 33.5, tensile strength 16.24MPa, elongation at break 185.6%.
Embodiment 3
100 parts of polrvinyl chloride, 30 parts of magnesium calcium powder, 9 parts of DOP, 18 parts of PCl, 9 parts of ESO, 4.5 parts of TCEP, 12 parts of ZB,
8 parts of calcium zinc stabilizer.
Test result, oxygen index (OI) OI are 30.2, tensile strength 15.68MPa, elongation at break 192.87%.
Embodiment 4
100 parts of polrvinyl chloride, 30 parts of magnesium calcium powder, 9 parts of DOP, 18 parts of PCl, 9 parts of ESO, Sb2O31.5 parts, 12 parts of ZB,
8 parts of calcium zinc stabilizer.
Test result, oxygen index (OI) OI are 35.9, tensile strength 16.78MPa, elongation at break 151.20%.
Embodiment 5
100 parts of polrvinyl chloride, 20 parts of magnesium calcium powder, 8 parts of DOP, 12 parts of PCl, Sb2O31 part, 5.5 parts of ZB, calcium zinc stabilizer
8 parts.
Test result, oxygen index (OI) OI are 43.9, tensile strength 37.2MPa, elongation at break 26.5%.
Embodiment 6
100 parts of polrvinyl chloride, 70 parts of magnesium calcium powder, 4 parts of DOP, 28 parts of PCl, Sb2O31.6 parts, 6.5 parts of ZB, calcium zinc are stable
8 parts of agent.
Test result, oxygen index (OI) OI are 44.9, tensile strength 17.7MPa, elongation at break 24.2%.
By test result, embodiment 1-4, meet in GB/T8815-2008 soft PVC plastic for electric wire and cable
The requirement of model J-70.That is tensile strength>15.0MPa, elongation at break>150%.Additionally, oxygen index (OI) OI>30, reach fire-retardant
Classification standard.
The adjustment of 6 formula of experimental example 5 and embodiment, can obtain that product tensile strength is bigger, and elongation at break is little, product
It is slightly hard, but oxygen index (OI) OI very high flame retardant products.
Table 1
Table 2
Adjusted by 2 cost price of table, converting into fire retardant PVC tons cost is：(1492/206) × 1000=7242.7 is first.No
But fire retardant effect is obtained, and cost is very low, has broad application prospects.
Embodiment 7
100 parts of polrvinyl chloride, 50 parts of magnesium calcium powder, 12 parts of DOP, 14 parts of PCl, 6 parts of ESO, 10 parts of TCEP, 6 parts of ZB,
8 parts of stabilizer.
Test result, oxygen index (OI) OI are 30.2, tensile strength 15.33MPa, elongation at break 150.68%.Meet GB/
The requirement of model J-90 in T8815-2008 soft PVC plastic for electric wire and cable.
Embodiment 8-22
Using 100 parts of polrvinyl chloride, 8 parts of stabilizer, superfine active magnesium calcium powder, DOP, PCl, ESO, TCEP, ZB are variable,
Experimental result such as table 3.
Table 3
Jing is more, and first once linear is returned, and obtains linear equation y1、y2、y3, Jing inspections, regression equation are equal in α=0.05 level
It is significantly correlated.
Oxygen index (OI) OI:
y1=66.8278+0.0058x1-0.2810x2-1.4384x3-0.2650x4+1.2886x5+0.0049x6
Tensile strength：
y2=23.2562-0.3993x1-0.1136x2+1.1514x3-0.1297x4+1.0716x5-1.6097x6
Percentage elongation：
y3=105.2405-2.2233x1+5.3507x2+4.1386x3+3.1006x4+4.2987x5-2.1701x6
Cost equation：
y4=1000 (1.2x1+13.8x2+7.2x3+12x4+12x5+12x6+7.8*100+14*6+14*2)/(100+x1+x2
+x3+x4+x5+x6+8)
It is assumed that limiting PVC100 parts, 40 parts of magnesium calcium powder, 6 parts of ESO, 10 parts of TCEP, you can obtain cost, DOP, PCl tri-
Person's graph of a relation (Fig. 3), can match certain formula according to pattern, such as if it is desired to oxygen index (OI) OI>30, tensile strength>
15.0Mpa, elongation at break>150%, A regions in can obtaining on figure, formula is selected in relatively low by left area cost, keeps right
Border area domain is relatively costly.Fixed other specification, is mapped by above-mentioned equation, can obtain corresponding pattern as a same reason, can be with
Suitable formula is selected therefrom.
Embodiment 23-35
100 parts of polrvinyl chloride, magnesium calcium powder b1 parts, DOP b2 parts, PClb3 parts, Sb2O3B4 parts, ZB b5 parts, stabilizer 8
Part.Oxygen index (OI) OI is y1, tensile strength y2MPa, elongation at break y3%.Test result such as table 4.
Table 4
Oxygen index (OI) OI experimental results carry out polynary linear return two times analyzing and processing, obtain regression equation：
a1=47.4339-0.1070b1-1.1375b2-0.1155b3+5.8960b4+0.8927b5+0.0010b1 2+
0.0151b2 2-0.0011b3 2-2.2683b4 2-0.0233b5 2
Tensile strength a2With elongation at break a3Experimental result carries out polynary once linear regression analyses and processes, and is returned
Equation：
a2=31.3977-0.1228b1-0.2507b2-0.1900b3+0.9582b4+0.4796b5
a3=56.4647-1.7059b1+4.3732b2+3.3350b3-12.1246b4-1.3706b5
PVC7800 yuan/ton of hypothetical cost, 1200 yuan/ton of superfine active magnesium calcium powder, 13800 yuan/ton of DOP, PCl
7200 yuan/ton, Sb2O338000 yuan/ton, 12000 yuan/ton of ZB, 14000 yuan/ton of stabilizer.Obtain cost equation：
a4=1000 (1.2b1+13.8b2+7.2b3+14b4+12b5+8*14+100*7.2)/(100+b1+b2+b3+b4+b5+
8)
Regression equation is used：Fixed 100 parts of polrvinyl chloride, 50 parts of magnesium calcium powder, Sb2O31 part, 5.5 parts of ZB, calcium zinc are stable
8 parts of agent.Require oxygen index (OI) OI>30, tensile strength >=15.0MPa, elongation at break >=150%.Can then be met above-mentioned
Cost price that condition is required, the scope of DOP and PCl, as shown in figure 4, meet above-mentioned condition shown in B regions in figure, from
It is visible in Fig. 4, it is lower the closer to left side cost.
In the same manner, the other specification such as fixing PVC, is mapped by above-mentioned equation, can obtain corresponding pattern as a same reason, can
Therefrom to select the suitable formula for oneself requiring.
Embodiment 36
100 parts of polrvinyl chloride, 70 parts of magnesium calcium powder, 4 parts of diethylene glycol ester, 2 parts of epoxy aliphatic acid methyl ester, 12 parts of DOP, PCl 8
Part, 2 parts of TCEP, 2 parts of ZB, 8 parts of calcium-zinc composite stabilizing agent.
Test result, oxygen index (OI) OI are 32.1, tensile strength 16.2MPa, elongation at break 161.4%.
Embodiment 37
100 parts of polrvinyl chloride, 50 parts of magnesium calcium powder, 10 parts of magnesium hydroxide, 5 parts of diphenyl 2 ethylhexyl phosphate, triaryl phosphate 3
Part, 9 parts of DOP, 9 parts of PCl, 4 parts of TCEP, 2 parts of ZB, 2 parts of Zinc Oxide, 8 parts of calcium-zinc composite stabilizing agent.
Test result, oxygen index (OI) OI are 31.6, tensile strength 15.9MPa, elongation at break 165.4%.
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various modifications or modification within the scope of the claims, this not shadow
Ring the flesh and blood of the present invention.
Claims (7)
1. a kind of fire retardant polychloroethylene composition, it is characterised in that including the following component counted by weight：
2. fire retardant polychloroethylene composition as claimed in claim 1, it is characterised in that the model of the Corvic
PVC-SG-5。
3. fire retardant polychloroethylene composition as claimed in claim 1, it is characterised in that the plasticizer is diethylene glycol hexichol first
At least one in acid esters, epoxy aliphatic acid methyl ester, dioctyl phthalate, diphenyl 2 ethylhexyl phosphate, triaryl phosphate.
4. a kind of preparation method of fire retardant polychloroethylene composition as claimed in claim 1, it is characterised in that including following step
Suddenly：
By Corvic, superfine active magnesium calcium powder, plasticizer, Firebrake ZB, antimony oxide, magnesium hydroxide, epoxy soybean
Oil, chlorinated paraffin, calcium-zinc composite stabilizing agent, phosphotriester, Zinc Oxide are mixed in being added to high-speed mixer, then carry out double roller
Plasticate, then tested after vulcanizer compression molding, after product is up to standard, blanking.
5. preparation method as claimed in claim 4, it is characterised in that the temperature that the double roller is plasticated is 160～180 DEG C.
6. the preparation method as described in claim 4 or 5, it is characterised in that the time that the double roller is plasticated is 8～10min.
7. preparation method as claimed in claim 4, it is characterised in that the temperature of the tabletting is 75～85 DEG C, tabletting when
Between be 4～6min.
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| CN106009419A (en) * | 2016-08-09 | 2016-10-12 | 叶伟然 | Novel graphene smoke-abatement flame-retardant PVC and preparation method thereof |
| CN106832656A (en) * | 2016-12-28 | 2017-06-13 | 滁州品之达电器科技有限公司 | A kind of Special material for flame-retardant polyvinyl chloride switch holder and preparation method thereof |
| CN107629360A (en) * | 2017-10-24 | 2018-01-26 | 博尔德南通汽车零部件有限公司 | A kind of formula and its processing technology of improvement PVC insulating materials fire resistances |
| CN110283401B (en) * | 2019-05-24 | 2021-06-25 | 广东联塑科技实业有限公司 | Low-cost low-precipitation soft PVC polyester yarn reinforced mesh tube material and preparation method thereof |
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