CN102382401B - CMR-grade high-flame-retardant polyvinyl chloride cable sheath material and preparation method thereof - Google Patents
CMR-grade high-flame-retardant polyvinyl chloride cable sheath material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a CMR-grade high-flame-retardant polyvinyl chloride cable sheath material which comprises the following components in parts by weight: 100 parts of polyvinyl chloride, 20-40 parts of plasticizer, 15-40 parts of flame retardant plasticizer, 40-80 parts of flame retardant, 6-10 parts of stabilizer and 1-5 parts of auxiliary agent; wherein the flame retardant plasticizer is a mixture of resorcinol bis (diphenyl phosphate), dioctyl tetrabromophthalate and tris (2, 3-dichloropropyl) phosphate; the weight ratio of the resorcinol bis (diphenyl phosphate), the dioctyl tetrabromophthalate and the tris (2, 3-dichloropropyl) phosphate is as follows: 3-6: 1. The invention also provides a preparation method of the sheath material. The cable sheath material can greatly reduce the using amount of common plasticizer, and effectively increase the flame retardant property of the product, thereby achieving the optimal combination point of processability and flame retardancy.
Description
Technical field
The present invention relates to a kind of cable jacket material, relate in particular to a kind of CMR level high flame retardant polyvinyl chloride cable sheath material and preparation method thereof.
Background technology
At present, along with the development of communication network, the increasing method that adopts comprehensive wiring in the commercial office block, this has caused the communication cable of top ceiling or space under floor more and more.In North America and Mexico, all communication cables must meet one of CMP, CMR, CM, four fire ratings of CMX, and sign must be arranged.
Wherein, CMR hierarchical communication cable is that grade occupy deputy cable, and applicable safety standards is UL1666.Experiment is defined on the simulation upright shafts and lays many samples, the 154.5KW coal gas Bunsen burner of usefulness regulation 30 minutes.Criterion of acceptability is the top that flame can not spread to 12 feet high rooms.CMR hierarchical communication cable does not have the smokescope standard, generally is used for floor vertically and the horizontal wiring use, one of flame-retardant cable that is most widely used.The CMR level communications cable has perfect fire retardancy, use stops the burning diffusion based on halid chemical substance, and CMR cable overcoat is generally made by certain class PVC, can give out hydracid class gas in the combustion chamber, gas can exhaust airborne oxygen, makes fray-out of flame.
At present, application PVC (polyvinyl chloride) is that the flame-retardant cable material of base-material is a lot, publication number is that the patent of invention of CN102161805A discloses a kind of CMR level high-flame-resistance environment-friendly concentric cable polyvinyl chloride cable sheathing compound,, to use PVC be base material to cable jacket material, be equipped with multiple softening agent, fire retardant, stablizer and weighting agent, obtain the flame-proof composite material that a kind of energy is used for CMR level coaxial cable sheath.This flame-proof composite material oxygen index is lower than 35, and flame retardant effect is limited, and purposes is limited on the coaxial cable sheath applicable.
Summary of the invention
The present invention provides high cable sheath material of a kind of oxygen index and preparation method thereof for solving the low technical problem of oxygen index of existing cable sheath material.
The invention provides a kind of CMR level high flame retardant polyvinyl chloride cable sheath material, this cable sheath material comprises
Wherein, described flame-retardant plasticizer is the mixture of Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP) and tricresyl phosphate (2,3-, two chloropropyls) ester; The weight ratio of described Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP) and tricresyl phosphate (2,3-, two chloropropyls) ester is: 3-6: 3-6: 1.
The present invention also provides a kind of preparation method of cable sheath material of the present invention, may further comprise the steps:
S1, preparation flame-retardant plasticizer mixture: Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP) and tricresyl phosphate (2,3-, two chloropropyls) ester are mixed;
S2, batching: polyvinyl chloride is poured in the high mixer, be heated to while stirring 90-100 ℃, the flame-retardant plasticizer mixture for preparing among the adding step S1 also stirs, and then adds softening agent and stirs, and adds at last fire retardant, stablizer and auxiliary agent and stirs;
S3, extruding pelletization: the mixture that obtains among the step S2 is joined the twin screw extruder granulation, namely obtain cable sheath material.
Cable sheath material of the present invention Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP) and tricresyl phosphate (2,3-two chloropropyls) the ester mixture that proportionally mixes formation is applied in the product as flame-retardant plasticizer, produce synergistic effect, can greatly reduce the consumption of common softening agent, effectively increase simultaneously the flame retardant properties of product, thereby reach the best joint of processibility and flame retardant resistance.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of CMR level high flame retardant polyvinyl chloride cable sheath material, this cable sheath material comprises
Wherein, described flame-retardant plasticizer is the mixture of Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP) and tricresyl phosphate (2,3-, two chloropropyls) ester; The weight ratio of described Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP) and tricresyl phosphate (2,3-, two chloropropyls) ester is: 3-6: 3-6: 1.
The present inventor draws through a large amount of experiments, cause the reason of all deficiencies of like product in the industry mainly to be, the flame-retardant sheath material of using in the CMR of line style grade products requires to have preferably processing characteristics, thereby also will have enough flame retardant resistances to reach harsh CMR grade combustion requirements simultaneously.And well-known, the processing characteristics of PVC mainly relies on the softening agent of interpolation q.s to realize, and common softening agent is inflammable substance, and the larger processibility of addition is better, but more easily burning; And reduce the processibility that its consumption certainly will reduce product, so that product is of poor quality, for following process is brought difficulty.Invention of the present invention is through the discovery of a large amount of experiment accidents, select Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP) and tricresyl phosphate (2,3-two chloropropyls) ester is 3-6: 3-6 according to weight ratio: 1 mixture that mix to form is as flame-retardant plasticizer, can obtain all good cable sheath materials of flame retardant resistance and plasticization capacity.Wherein, two (diphenyl phosphoester) flame retardant resistances of Resorcinol are better, and tetrabormated dioctyl phthalate (DOP) soffening is better.But above two kinds because molecular structure differs larger, and mutual solubility is relatively poor, and the existing phosphoric acid ester group of tricresyl phosphate (2,3-, two chloropropyls) ester has again the halogenation group, with above-mentioned both have preferably consistency, increased both mutual solubilities as a bridge block.Great many of experiments through the contriver is also found, above-mentioned three kinds of flame-retardant plasticizers are applied in the product proportionally mixing, and produce synergistic effect, can greatly reduce the consumption of common softening agent, effectively increase simultaneously the flame retardant properties of product, thereby reach the best joint of processibility and flame retardant resistance.
In order further to improve processing characteristics and the flame retardant properties of cable sheath material, preferably, the weight ratio of described Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP)s, tricresyl phosphate (2,3-, two chloropropyls) ester is: 3.5-5.5: 3.5-5.5: 1.
Cable sheath material provided by the present invention, described softening agent has no particular limits, and can be various softening agent commonly used in this area, at least a as in Di Iso Decyl Phthalate, trioctyl trimellitate, the dioctyl terephthalate.
Cable sheath material provided by the present invention, described fire retardant has no particular limits, and can be various fire retardants commonly used in this area, and fire retardant is at least a in antimonous oxide and aluminium hydroxide, magnesium hydroxide, the zinc borate as described.
Preferably, described auxiliary agent is at least a in polyethylene wax, stearic acid, silicone, the Methylacrylate-Acrylate Copolymer.
Preferably, stablizer is commercially available calcium zinc stabilizer.
The present invention also provides the preparation method of this cable sheath material, may further comprise the steps:
S1, preparation flame-retardant plasticizer mixture: Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP) and tricresyl phosphate (2,3-, two chloropropyls) ester are mixed;
S2, batching: polyvinyl chloride is poured in the high mixer, be heated to while stirring 90-100 ℃, the flame-retardant plasticizer mixture for preparing among the adding step S1 also stirs, and then adds softening agent and stirs, and adds at last fire retardant, stablizer and auxiliary agent and stirs;
S3, extruding pelletization: the mixture that obtains among the step S2 is joined the twin screw extruder granulation, namely obtain cable sheath material.
Preferably, the working temperature of described twin screw extruder is 140 ℃-160 ℃, and the feeding frequency is 20 hertz, and engine speed is 300 rev/mins.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
1, weighing: weigh respectively tie substance according to following table 1 embodiment 1 described prescription for subsequent use;
2, preparation flame-retardant plasticizer mixture: load weighted Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP)s, tricresyl phosphate (2,3-, two chloropropyls) ester are added in the stirring tank, be stirred well to evenly miscible for subsequent use;
3, batching: polyvinyl chloride is poured in the high mixer, be heated to while stirring 100 ℃, add the mixed solution for preparing in the step 2, stir 5min, add load weighted softening agent, restir 5min; Then add successively all the other fire retardants, stablizer and auxiliary agent, high-speed stirring evenly gets final product.
4, extruding pelletization: the above-mentioned material that will mix that will prepare discharges, drops into the feed hopper of twin screw extruder from mixer, evenly add in the twin screw extruder by feeding machine, the twin screw extruder Temperature Setting is between 1500 ℃, the feeding frequency is 20 hertz, engine speed is 300 rev/mins, through screw extrusion press high speed shear, mixing, reaches the purpose of abundant consolute, make material by the stock cutter of head again, sending into the feed bin packing by blower fan can sample A1.
Table 1
Embodiment 2-7
Content according to each prescription of embodiment 2-6 in the method for embodiment 1 and the table 1 prepares sample A2-A6.
Comparative Examples 1
Prepare sample CA1 according to the method among the CN102161805A.
Comparative Examples 2
Method according to embodiment 1 prepares sample CA2, and difference is: do not contain Resorcinol two (diphenyl phosphoester).
Comparative Examples 3
Method according to embodiment 1 prepares sample CA3, and difference is: do not contain the tetrabormated dioctyl phthalate (DOP).
Comparative Examples 4
Method according to embodiment 1 prepares sample CA4, and difference is: do not contain tricresyl phosphate (2,3-, two chloropropyls) ester.
Testing method
The sample A1-A6 of embodiment 1-6 and the sample CA1-CA4 of Comparative Examples 1-4 are carried out the test of following 1-5 project, the results are shown in Table 2.The sample CA1-CA4 of the sample A1-A6 of embodiment 1 and Comparative Examples 1-4 at 100 ℃ of aging 168h, then to its test of carrying out the 4-6 project, be the results are shown in Table 3.
1, shore hardness
Shore hardness according to a standard A STM D-2240 test sample;
2, melting index
Melting index according to standard A STM D-1238 specimen;
3, oxygen index
Oxygen index according to standard A STM D-2863 specimen;
4, tensile break strength
Tensile break strength according to standard A STM D-412 specimen;
5, tension fracture elongation rate
Tension fracture elongation rate according to standard A STM D-412 specimen;
6, CMR grade combustion testing result
CMR standard according to UL1666 is tested sample.
Table 2
Table 3
As can be seen from Table 2, the sheath material that the present invention obtains is in the situation that significantly subdued common plasticizer consumption, and the melting index of product is higher, shows that processing characteristics does not reduce, and oxygen index has all reached more than 38, shows that flame retardant properties increases substantially.And the oxygen index of Comparative Examples is lower than 33.4, and flame retardant properties is poor.
As can be seen from Table 3, sheath material of the present invention can satisfy the combustion testing of CMR grade fully.Only have Comparative Examples 1 can pass through the combustion testing of CMR grade in the Comparative Examples, but its tensile break strength is still far short of what is expected than embodiment with tension fracture elongation rate, and Comparative Examples 2-4 all can not be by the combustion testing of CMR grade.
Specific embodiment described in the present invention only is to the explanation for example of the present invention's spirit.Those skilled in the art can make various modifications or replenish or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made a detailed description and has quoted as proof some specific embodiments, to those skilled in the art, only otherwise it is obvious leaving that the spirit and scope of the present invention can make various changes or revise.
Claims (6)
1. a CMR level high flame retardant polyvinyl chloride cable sheath material is characterized in that, this cable sheath material comprises the material that contains following weight part:
Wherein, described softening agent is at least a in Di Iso Decyl Phthalate, trioctyl trimellitate and the dioctyl terephthalate; Described flame-retardant plasticizer is the mixture of Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP) and tricresyl phosphate (2,3-, two chloropropyls) ester; The weight ratio of described Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP) and tricresyl phosphate (2,3-, two chloropropyls) ester is: 3-6:3-6:1.
2. cable sheath material according to claim 1 is characterized in that, the weight ratio of described Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP) and tricresyl phosphate (2,3-, two chloropropyls) ester is: 3.5-5.5:3.5-5.5:1.
3. cable sheath material according to claim 1 is characterized in that, described fire retardant is at least a in antimonous oxide, aluminium hydroxide, magnesium hydroxide and the zinc borate.
4. cable sheath material according to claim 1 is characterized in that, described auxiliary agent is at least a in polyethylene wax, stearic acid, silicone and the Methylacrylate-Acrylate Copolymer.
5. the preparation method of a cable sheath material claimed in claim 1 is characterized in that, may further comprise the steps:
S1, preparation flame-retardant plasticizer mixture: Resorcinol two (diphenyl phosphoester), tetrabormated dioctyl phthalate (DOP) and tricresyl phosphate (2,3-, two chloropropyls) ester are mixed;
S2, batching: polyvinyl chloride is poured in the high mixer, be heated to while stirring 90-100 ℃, the flame-retardant plasticizer mixture for preparing among the adding step S1 also stirs, and then adds softening agent and stirs, and adds at last fire retardant, stablizer and auxiliary agent and stirs;
S3, extruding pelletization: the mixture that obtains among the step S2 is joined the twin screw extruder granulation, namely obtain cable sheath material.
6. preparation method according to claim 5 is characterized in that, the working temperature of described twin screw extruder is 140 ℃-160 ℃, and the feeding frequency is 20 hertz, and engine speed is 300 rev/mins.
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| CN201110326785.8A CN102382401B (en) | 2011-10-25 | 2011-10-25 | CMR-grade high-flame-retardant polyvinyl chloride cable sheath material and preparation method thereof |
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| CN201110326785.8A CN102382401B (en) | 2011-10-25 | 2011-10-25 | CMR-grade high-flame-retardant polyvinyl chloride cable sheath material and preparation method thereof |
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| CN103374186A (en) * | 2012-04-17 | 2013-10-30 | 鲍联 | Low-smoke fire-retardant PVC (polyvinyl chloride) cable material |
| CN102915794A (en) * | 2012-11-16 | 2013-02-06 | 中利科技集团（辽宁）有限公司 | Control signal electric power composite cable for airport |
| CN102993602B (en) * | 2012-11-27 | 2014-08-06 | 宁波一舟塑胶有限公司 | CMP-grade flame-retardant smoke-inhibiting polyvinyl chloride cable sheath material and preparation method thereof |
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| CN105505408A (en) * | 2015-12-08 | 2016-04-20 | 佛山华清智业环保科技有限公司 | Flame retardant |
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| CN110951189B (en) * | 2019-12-12 | 2021-05-14 | 上海凯波电缆特材股份有限公司 | Polyvinyl chloride material and preparation method thereof |
| CN112480534A (en) * | 2020-11-26 | 2021-03-12 | 上海明克包装制品有限公司 | Heat-resistant flame-retardant paper-plastic composite bag and preparation method thereof |
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| US4892683A (en) * | 1988-05-20 | 1990-01-09 | Gary Chemical Corporation | Flame retardant low smoke poly(vinyl chloride) thermoplastic compositions |
| US5036121A (en) * | 1988-09-06 | 1991-07-30 | The B. F. Goodrich Company | Flame and smoke retardant cable insulation and jacketing compositions |
| US7109260B2 (en) * | 2002-10-17 | 2006-09-19 | Ciba Specialty Chemicals Corporation | Flame retardant compositions |
| CN102161805A (en) * | 2011-05-28 | 2011-08-24 | 临安市普发电缆材料有限公司 | Polyvinyl chloride cable sheath material for CMR-grade high-flame-retardant environment-friendly coaxial cable |
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