CN104341678A - Intumescent flame retardant waterproof polypropylene composite material - Google Patents
Intumescent flame retardant waterproof polypropylene composite material Download PDFInfo
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- CN104341678A CN104341678A CN201410553004.2A CN201410553004A CN104341678A CN 104341678 A CN104341678 A CN 104341678A CN 201410553004 A CN201410553004 A CN 201410553004A CN 104341678 A CN104341678 A CN 104341678A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention relates to an intumescent flame retardant waterproof polypropylene composite material. The intumescent flame retardant waterproof polypropylene composite material comprises the following components by mass percent: 70-90% of polypropylene resin, 8-25% of intumescent flame retardant and 0-5% of flame retardant synergist, wherein the intumescent flame retardant is formed by ammonium polyphosphate II with the degree of polymerization not less than 1000 and a triazine hyperbranched char-forming agent in a mass ratio of (3 to 1)-(1 to 3). The intumescent flame retardant waterproof polypropylene composite material has the advantages that the polypropylene material has higher heat stability and begins to be slowly dissolved at about 320 DEG C; meanwhile, the composite material can achieve excellent flame retardant effects and has higher flame retardance efficiency by using lower content of the flame retardant, thus reducing the production cost of the composite material; compared with the prior art, the material also has better waterproofness, and after being soaked in a water bath at 70 DEG C for 168 hours, the material can still achieve the V-0 rating through a UL-94 test.
Description
Technical field
the invention belongs to flame-proof composite material technical field, be specifically related to the water-fast polypropylene composite material of a kind of expansion type flame-retarding, it has excellent flame retardant resistance, thermostability and water tolerance.
Background technology
polypropylene (PP) is as one of five large general-purpose plastics, there is the performance such as good mechanical property, processing characteristics, electrical insulating property, lower temperature resistance, chemical stability, easily machine-shaping, and it is cheap, be widely used in the every field such as industry, agricultural, household electrical appliance, textile industry, communications and transportation, become one of material indispensable in people's daily life.But, because polyacrylic limiting oxygen index(LOI) is very low, only have 18, belong to inflammable material, produce a large amount of molten drops during burning, make propagation of flame, fire hazard is comparatively large, cannot meet the service requirements of certain material at fire protection field, makes it apply by restriction to a certain extent.Therefore, be necessary to carry out flame-retardant modified to polypropylene.General toward wherein adding fire retardant, being usually used in polyacrylic fire retardant has three major types: metal hydroxides, halogen containing flame-retardant and expansion type flame retardant (IFR).IFR is one of environment-friendly flame retardant agent type of widespread use in recent years, it not only overcomes the shortcoming that halogenated flame retardant easily releases pungency and corrosive gas and smog when burning, many molten drops, the easily personnel that cause suffocate, and also overcomes inorganic combustion inhibitor because addition is greatly to the detrimentally affect that the mechanics of materials, processibility the subject of knowledge and the object of knowledge bring.Expansion type flame retardant can prevent the characteristics such as polymkeric substance molten drop effectively because of the layer of charcoal of the fire retardant mechanism of its uniqueness and Halogen, low cigarette, low toxicity, generation, meets the requirement of preserving the ecological environment now.
generally speaking, IFR comprises 3 parts, i.e. carbon source (being often polyol, as tetramethylolmethane), acid source (as ammonium polyphosphate) and source of the gas (as trimeric cyanamide).In traditional expanded flame-retardant polypropylene matrix material, Intumescent Retardant System generally selects polyphosphoric acid amine-tetramethylolmethane-trimeric cyanamide system, tetramethylolmethane (PER) is a kind of compound of strong polarity, in use there is a lot of shortcoming, as bad with polypropylene-base compatability, easily reunite, cause the water-fast poor durability of material etc.Therefore, the anti-flaming polypropylene material developing water-fast good endurance is engineering technical personnel's problem demanding prompt solution of macromolecule modified Material Field.
Summary of the invention
the present invention is intended to overcome deficiency of the prior art, provides that a kind of flame retardant properties is good, thermostability is high and the water-fast polypropylene composite material of the expansion type flame-retarding of water-tolerant.
for solving above technical problem, the technical scheme that the present invention takes is:
the water-fast polypropylene composite material of a kind of expansion type flame-retarding, by mass percentage, described expansion type flame-retarding is water-fast, and polypropylene composite material consists of the following composition: 70-90% acrylic resin, 8-25% expansion type flame retardant and 0-5% fire retarding synergist; Described expansion type flame retardant by ammonium polyphosphate and the hyperbranched char-forming agent of triazines in mass ratio 3:1 ~ 1:3 form, wherein said ammonium polyphosphate is II type ammonium polyphosphate of the polymerization degree>=1000, and the structural formula of the hyperbranched char-forming agent of described triazines is as follows:
wherein, the Z aryl that to be NH or N, R be with alkyl between piperazine ring, straight chained alkyl, aryl or multiple phenyl ring.
in flame retardant area, ammonium polyphosphate is divided into I type ammonium polyphosphate and II type ammonium polyphosphate, I type ammonium polyphosphate has the linear chain of different lengths, and decomposition temperature is lower, water-soluble higher, the usual polymerization degree is less than 100, and II type ammonium polyphosphate is a kind of slightly water-soluble material, the polymerization degree can reach 1000, even larger, Heat stability is good, general decomposition temperature is at 300 DEG C or more.The present invention selects II type ammonium polyphosphate and the hyperbranched char-forming agent of triazines to form composite flame retardant system, make both on decomposition temperature, molecular structure, reach good matching degree, system can form fine and close foamed char in combustion, in combustion can effectively starvation and heat, hinder inner base to burn further.
preferably, described fire retarding synergist is one or more the mixing in polynite, diatomite, metal hydroxides, 4A molecular sieve, zinc borate and nano silicon.
preferably, described polypropylene is homo-polypropylene or modification by copolymerization polypropylene, in polypropylene molecular chain, namely have a small amount of ethene segment to carry out modification to polypropylene.
due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
expansion type flame-retarding of the present invention is water-fast, and polypropylene composite material thermostability is higher, just starts slow decomposition, use the fire retardant of lower aq simultaneously when about 320 DEG C, and just can reach excellent flame retardant effect, flame retarding efficiency is higher, reduces the production cost of matrix material; Compared with prior art, material of the present invention also has better water tolerance, and material is after 70 DEG C of water-baths soak 168 hours, and UL-94 test still can reach V-0 rank.
Embodiment
below in conjunction with specific embodiment, the present invention will be further described in detail, but be not limited to these embodiments.
the structural formula of the hyperbranched char-forming agent of triazines used in the embodiment of the present invention is as follows respectively:
formula I;
formula II;
formula III;
the various testing standards of testing institute's foundation in the present invention are as follows:
vertical combustion test (UL-94): ASTM D3801-1996
oxygen index test (LOI): ASTM D2863
embodiment 1
the water-fast polypropylene composite material of expansion type flame-retarding of the present embodiment, is processed through twin-screw extrusion by following component: 80 parts of homo-polypropylene resins, 15 part of II type ammonium polyphosphate, the hyperbranched char-forming agent of triazines shown in 5 parts of formulas I.
obtained material is under air conditions, and temperature during thermal weight loss 5% is 300 DEG C, and carbon left when 600 DEG C is 24.6%; Through oxygen index and vertical combustion test, to obtain LOI be 32.5, UL94 is V-0 rank; After material is soaked 168 hours (week age) under 70 DEG C of water-baths, then carry out oxygen index and vertical combustion test experiments, LOI value is that 30, UL-94 still can reach V-0 rank.
embodiment 2
the water-fast polypropylene composite material of expansion type flame-retarding of the present embodiment, is processed through twin-screw extrusion by following component: 70 parts of acrylic resin copolymer, 18 part of II type ammonium polyphosphate, the hyperbranched char-forming agent of triazines shown in 7 parts of formulas II, 3 parts of polynites.
through oxygen index and vertical combustion test, to obtain LOI be 33.5, UL94 to obtained material is V-0 rank; Temperature under air conditions during thermal weight loss 5% is 318 DEG C, and carbon left when 600 DEG C is 22.1%; After material is soaked 168 hours (week age) under 70 DEG C of water-baths, then carry out oxygen index and vertical combustion test experiments, LOI value is that 31.5, UL-94 still can reach V-0 rank.
embodiment 3
the water-fast polypropylene composite material of expansion type flame-retarding of the present embodiment, is processed through twin-screw extrusion by following component: 90 parts of homo-polypropylene resins, 4 part of II type ammonium polyphosphate, the hyperbranched char-forming agent of triazines shown in 4 parts of formulas III, 2 parts of 4A molecular sieves.
through oxygen index and vertical combustion test, to obtain LOI be 29.5, UL94 to obtained material is V-0 rank; Temperature under air conditions during thermal weight loss 5% is 342 DEG C, and carbon left when 600 DEG C is 25.7%; After material is soaked 168 hours (week age) under 70 DEG C of water-baths, then carry out oxygen index and vertical combustion test experiments, LOI value is that 27.5, UL-94 still can reach V-0 rank.
embodiment 4
the water-fast polypropylene composite material of expansion type flame-retarding of the present embodiment, is processed through twin-screw extrusion by following component: 70 parts of acrylic resin copolymer, 6 part of II type ammonium polyphosphate, the hyperbranched char-forming agent of triazines shown in 19 parts of formulas I, 2 parts of 4A molecular sieves.
through oxygen index and vertical combustion test, to obtain LOI be 34, UL94 to obtained material is V-0 rank; Temperature under air conditions during thermal weight loss 5% is 330 DEG C, and carbon left when 600 DEG C is 30.6%; After material is soaked 168 hours (week age) under 70 DEG C of water-baths, then carry out oxygen index and vertical combustion test experiments, LOI value is that 31.5, UL-94 still can reach V-0 rank.
embodiment 5
the water-fast polypropylene composite material of expansion type flame-retarding of the present embodiment, is processed through twin-screw extrusion by following component: 85 parts of homo-polypropylene resins, 9 part of II type ammonium polyphosphate, the hyperbranched char-forming agent of triazines shown in 3 parts of formulas II, 2 parts of zinc borates and 1 part of nano silicon.
through oxygen index and vertical combustion test, to obtain LOI be 31, UL94 to obtained material is V-0 rank; Temperature under air conditions during thermal weight loss 5% is 304 DEG C, and carbon left when 600 DEG C is 21.5%; After material is soaked 168 hours (week age) under 70 DEG C of water-baths, then carry out oxygen index and vertical combustion test experiments, LOI value is that 27.5, UL-94 still can reach V-0 rank.
polypropylene composite material that expansion type flame-retarding obtained by the present invention is water-fast, fire retardant addition just can reach good flame retardant effect in 5 ~ 25 scopes, the production cost of anti-flaming polypropylene material can be reduced, Heat stability is good simultaneously, charring rate high (at 600 DEG C, carbon left reaches 20% ~ 40%) under high temperature, still can reach the fire-retardant rank of V-0 soak one week under hot water bath after, there is extraordinary water tolerance.
above to invention has been detailed description; its object is to allow the personage being familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence change that all spirit according to the present invention are done or modification, all should be encompassed in protection scope of the present invention.
Claims (3)
1. the water-fast polypropylene composite material of expansion type flame-retarding, it is characterized in that: by mass percentage, described expansion type flame-retarding is water-fast, and polypropylene composite material consists of the following composition: 70-90% acrylic resin, 8-25% expansion type flame retardant and 0-5% fire retarding synergist; Described expansion type flame retardant by ammonium polyphosphate and the hyperbranched char-forming agent of triazines in mass ratio 3:1 ~ 1:3 form, wherein said ammonium polyphosphate is II type ammonium polyphosphate of the polymerization degree >=1000, and the structural formula of the hyperbranched char-forming agent of described triazines is as follows:
Wherein, the Z aryl that to be NH or N, R be with alkyl between piperazine ring, straight chained alkyl, aryl or multiple phenyl ring.
2. the water-fast polypropylene composite material of expansion type flame-retarding according to claim 1, is characterized in that: described fire retarding synergist is one or more the mixing in polynite, diatomite, metal hydroxides, 4A molecular sieve, zinc borate and nano silicon.
3. the water-fast polypropylene composite material of expansion type flame-retarding according to claim 1, is characterized in that: described polypropylene is homo-polypropylene or modification by copolymerization polypropylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410553004.2A CN104341678A (en) | 2014-10-17 | 2014-10-17 | Intumescent flame retardant waterproof polypropylene composite material |
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| CN201410553004.2A CN104341678A (en) | 2014-10-17 | 2014-10-17 | Intumescent flame retardant waterproof polypropylene composite material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106939095A (en) * | 2017-03-31 | 2017-07-11 | 江苏坤宇集团有限公司 | Flame-retardant compounds based on three piperazine triazine carbon forming agents |
| CN107022147A (en) * | 2017-05-19 | 2017-08-08 | 天津职业技术师范大学 | A kind of nano silicon and expanding fire retardant synergistic polypropylene flame redardant/ternary ethlene propyene rubbercompound material and preparation method thereof |
| CN108822400A (en) * | 2018-06-02 | 2018-11-16 | 山东兄弟科技股份有限公司 | A kind of dedicated resistance to preparation method that halogen-free flame retardants is precipitated of polypropylene |
| CN108866668A (en) * | 2018-05-28 | 2018-11-23 | 泽塔纳米科技（苏州）有限公司 | A kind of nano flame-retardant fiber and preparation method thereof |
| CN111808404A (en) * | 2020-07-20 | 2020-10-23 | 山东兄弟科技股份有限公司 | Intumescent flame retardant taking seek succinic acid polyester as char-forming agent |
| CN112322167A (en) * | 2020-11-13 | 2021-02-05 | 清远市普塞呋磷化学有限公司 | Intumescent steel structure fireproof coating |
| CN113845725A (en) * | 2021-10-19 | 2021-12-28 | 青岛塑科高分子科技有限公司 | Flame-retardant polypropylene material with good water resistance and preparation method thereof |
-
2014
- 2014-10-17 CN CN201410553004.2A patent/CN104341678A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106939095A (en) * | 2017-03-31 | 2017-07-11 | 江苏坤宇集团有限公司 | Flame-retardant compounds based on three piperazine triazine carbon forming agents |
| CN107022147A (en) * | 2017-05-19 | 2017-08-08 | 天津职业技术师范大学 | A kind of nano silicon and expanding fire retardant synergistic polypropylene flame redardant/ternary ethlene propyene rubbercompound material and preparation method thereof |
| CN108866668A (en) * | 2018-05-28 | 2018-11-23 | 泽塔纳米科技（苏州）有限公司 | A kind of nano flame-retardant fiber and preparation method thereof |
| CN108866668B (en) * | 2018-05-28 | 2021-02-19 | 泽塔纳米科技（苏州）有限公司 | Nano flame-retardant fiber and preparation method thereof |
| CN108822400A (en) * | 2018-06-02 | 2018-11-16 | 山东兄弟科技股份有限公司 | A kind of dedicated resistance to preparation method that halogen-free flame retardants is precipitated of polypropylene |
| CN108822400B (en) * | 2018-06-02 | 2021-04-06 | 山东兄弟科技股份有限公司 | Preparation method of precipitation-resistant halogen-free flame retardant special for polypropylene |
| CN111808404A (en) * | 2020-07-20 | 2020-10-23 | 山东兄弟科技股份有限公司 | Intumescent flame retardant taking seek succinic acid polyester as char-forming agent |
| CN111808404B (en) * | 2020-07-20 | 2022-06-14 | 山东兄弟科技股份有限公司 | Intumescent flame retardant taking seek succinic acid polyester as char-forming agent |
| CN112322167A (en) * | 2020-11-13 | 2021-02-05 | 清远市普塞呋磷化学有限公司 | Intumescent steel structure fireproof coating |
| CN113845725A (en) * | 2021-10-19 | 2021-12-28 | 青岛塑科高分子科技有限公司 | Flame-retardant polypropylene material with good water resistance and preparation method thereof |
| CN113845725B (en) * | 2021-10-19 | 2023-03-21 | 青岛塑科高分子科技有限公司 | Flame-retardant polypropylene material with good water resistance and preparation method thereof |
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