CN105566811A - Composite halogen-free flame-retardant smoke suppression agent of PVC wood-plastic composite material and preparation method and application of agent - Google Patents
Composite halogen-free flame-retardant smoke suppression agent of PVC wood-plastic composite material and preparation method and application of agent Download PDFInfo
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K5/00—Use of organic ingredients
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- C08K5/053—Polyhydroxylic alcohols
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention relates to a composite halogen-free flame-retardant smoke suppression agent of a PVC wood-plastic composite material and a preparation method and application of the agent, which relate to the composite halogen-free flame-retardant smoke suppression agent and the preparation method and application of the agent, and aim at solving the problems that the PVC wood-plastic composite material is combustible, a great amount of smoke is produced when the composite material is combusted, the addition amount of the existing PVC wood-plastic composite material flame-retardant smoke suppression agent is large, the flame-retardant effect and the smoke suppression effect are poor, and the existing PVC wood-plastic composite material flame-retardant smoke suppression agent is harmful to the health of people. The composite halogen-free flame-retardant smoke suppression agent consists of ammonium polyphosphate, melamine, pentaerythritol and copper oxide. The preparation method comprises the following steps: I, preparing an expansion-type flame-retardant agent; II, preparing the composite halogen-free flame-retardant smoke suppression agent. The application method comprises the following steps: I, weighing raw materials; II, preparing high-temperature materials; III, preparing a premix; IV, extruding and forming. The flame-retardant smoke suppression agent solves the problems that the wood-plastic composite material is combustible, a great amount of smoke is produced when the composite material is combusted, the addition amount of the existing flame-retardant smoke suppression agent is large, the effect is poor, and the existing flame-retardant smoke suppression agent is harmful to the health of people. The composite halogen-free flame-retardant smoke suppression agent is used for resisting the combustion and suppressing the smoke of the PVC wood-plastic composite material.
Description
Technical field
The present invention relates to anti-flaming smoke-inhibiting agent of a kind of PVC wood plastic composite material and its preparation method and application, be particularly suitable for wood fibre content 30% ~ 70% PVC wood plastic composite material fire-retardant and press down cigarette.
Background technology
Wood plastic composite is the matrix material manufactured for raw material with lignocellulosic material (as lignified filamentary materials such as timber, bamboo wood, agricultural crop straw and industrial wood wastes, its main chemical compositions is Mierocrystalline cellulose, hemicellulose and xylogen) and plastics (as thermal plasticity high polymers such as polyethylene, polypropylene, polystyrene, polyvinyl chloride).PVC wood plastic composite material is one of its principal item.PVC wood plastic composite material is due to its good processing characteristics, mechanical property and price advantage, and especially excellent woodiness touch, Application Areas constantly expands.Polyvinyl chloride resin itself belongs to non-combustible material, but owing to using a large amount of wood fibre fillers in PVC wood plastic composite material, when making material combustion, oxygen index obviously declines.Meanwhile, owing to producing a large amount of black smoke and toxic gas when polyvinyl chloride resin burns, when fire occurs, very large harm is caused to personnel, therefore, as finishing material, particularly house decorative material all requires that material has certain flame-proof smoke-suppressing, to reduce the danger of presence of fire.Suppress material combustion, the common method improving its flame retardant resistance adds fire retardant in material.
The compound of some halogenated flame as organic bromine is often used as the flame retardant properties improving polymkeric substance, but due to its burning insufficient, generally increase the generating rate of cigarette and carbon monoxide, and flue dust and poisonous gas are the major reasons causing personal injury in fire.
For the flame-retardant smoke inhibition of pure PVC, think that the effect of use metal oxide is better.Once use ANTIMONY TRIOXIDE SB 203 99.8 PCT as fire retardant the earliest in a large number, although it has good fire retardation, produce a large amount of cigarettes in combustion.Other some metal oxides, as some metal oxides of zinc system, iron system, copper system and molybdenum system, they can the mode of degrading of change PVC in various degree, promote the crosslinked of carbon skeleton, improve neat coal amout, because the price of metallic compound is higher, limit its a large amount of uses.
With the inorganic hydroxide fire retardant that magnesium hydroxide and aluminium hydroxide are representative, two aspect problems are had to limit them as the application of fire retardant in PVC wood plastic composite material.One is that the decomposition temperature of aluminium hydroxide is relatively low, two is to obtain enough flame retardant propertiess, usual addition up to 40% ~ 60%, loading level is large must cause resin mixing and shaping time material poor fluidity, affect Drawing abillity and mechanical property.Although magnesium hydroxide is the efficiently smoke filler of material, its decomposition temperature, at 340 DEG C ~ 490 DEG C, is better than aluminium hydroxide to the charing fire retardation of polymkeric substance, the loading level that same needs are larger.Meanwhile, the acid resistance of magnesium hydroxide is poor, can dissolve very soon, also easily make by lactic acid affects product surface leave fingerprint in acid.Therefore, the high-content of this type fire retardant adds and not only causes the high-density of the finished product and the disappearance of elastic performance, and can bring mixing, extrudes the problem of aspect, especially greatly limit the consumption of lignocellulosic material.
Zinc borate is considered to a kind of desirable anti-flaming smoke-inhibiting agent.Zinc borate is joined in wood powder/PVC matrix material, tapered calorimeter experiment test shows, zinc borate plays very important effect for the mass loss reducing material, there is good flame-retardant smoke inhibition effect simultaneously, but it add the Young's modulus and rupture modulus that reduce material, add water absorbability.
Some halogenated flame, as the compound of organic bromine, chlorinatedpolyethylene are often used as the flame retardant properties improving polymkeric substance, but generally increase the generating rate of cigarette and carbon monoxide due to the insufficient of its burning, and flue dust and poisonous gas are the major reasons causing personal injury in fire.
Mostly nano flame retardant smoke suppressant is oxide compound (CuO, ZnO, Fe
2o
3deng) and composite oxides, the liquid phase method of nanoparticle is prepared in the many employings of its method prepared, and is also current a kind of comparatively conventional method by intercalation (cationic exchange) legal system for nanometer presoma.Nano type anti-flaming smoke-inhibiting agent overcomes that traditional anti-flaming smoke-inhibiting agent addition is large, the shortcoming of flame-retardant smoke inhibition DeGrain, but the method technical sophistication, cost is higher.
Nanoclay particle being added with in wood plastic composite helps improve its mechanical strength, the flame retardant properties of matrix material also has certain improvement simultaneously, but the cost of this method is high, the flame retardant properties of matrix material is difficult to meet actual needs, and thus its practical application is subject to serious restriction.
Expansion type flame retardant be a class usually with P, N, C for principal element, the composite fire retardant be made up of acid source (dewatering agent), source of the gas (swelling agent) and carbon source (char-forming agent) three part, can be used for multiple combustible polymers material.Typical Intumescent Retardant System is that tetramethylolmethane (carbon source), polyphosphoric acid are by (acid source) and trimeric cyanamide (source of the gas).When adding the polymer materials burning of expansion type flame retardant, understand at table and form the uniform carbonaceous foam layer of one deck, this layer of charcoal is on good terms in cohesion and is played heat insulation, oxygen barrier, press down cigarette and anti-ly melt the effect of dripping, and Halogen, low cigarette, low toxicity, non-corrosiveness gas, thus expansion type flame retardant not only has very high fire-retardant effect, and environmental friendliness.Therefore, as new halogen-free flame-retardant system, expandable flame retardant technology has become one of fire-retardant research field enlivened very much.But this compound system is applied to separately in wood powder/PVC matrix material, DeGrain when adding a small amount of, and addition reaches 30 ~ 40 parts, not only increases cost and seriously reduce the mechanical property of material.Not yet realize in prior art pressing down cigarette modification to PVC wood plastic composite material, and smoke suppressing is particularly important for the indoor application of PVC wood plastic composite material.
Halogen-free flame-retardant wood-plastic composite material disclosed in existing patent, flame-retarding smoke-inhibiting PVC wood plastic matrix material, fire retardant or anti-flaming smoke-inhibiting agent exist PVC wood plastic composite material processor performance generation infringement, affect the problems such as material appearance, materials processing cost is high, smoke suppressing effect is undesirable, intermediate is wayward.
Summary of the invention
The present invention will solve the problem that PVC wood plastic composite material is flammable, burning produces a large amount of dense smoke, existing PVC wood plastic composite material anti-flaming smoke-inhibiting agent addition is large, fire-retardant and smoke suppressing effect is poor and existing halogenated flame retardant, lead salt fire retardant etc. are harmful to environment and health of people, provides a kind of PVC wood plastic composite material composite halogen-free anti-flaming smoke-inhibiting agent and its preparation method and application.
The composite halogen-free anti-flaming smoke-inhibiting agent of PVC wood plastic composite material of the present invention, be made up of polyphosphoric acid amine, trimeric cyanamide, tetramethylolmethane and cupric oxide, be in mass ratio: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(0.4 ~ 4): (0.3 ~ 3): (0.3 ~ 3): 1; Described cupric oxide is fire retarding synergist; Described polyphosphoric acid amine, trimeric cyanamide and tetramethylolmethane composition expansion type flame retardant, wherein the polymerization degree n > 1500 of ammonium polyphosphate;
The preparation method of described PVC wood plastic composite material composite halogen-free anti-flaming smoke-inhibiting agent carries out according to the following steps:
One, be in mass ratio: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(0.4 ~ 4): (0.3 ~ 3): (0.3 ~ 3): 1 takes polyphosphoric acid amine, trimeric cyanamide, tetramethylolmethane and cupric oxide as raw material, the polyphosphoric acid amine, trimeric cyanamide and the tetramethylolmethane that take are placed in high-speed mixer, under 2000r/min ~ 2500r/min rotating speed, stir 10min ~ 15min, namely complete the preparation of expansion type flame retardant;
Two, cupric oxide step one taken is as fire retarding synergist, join in the expansion type flame retardant of preparation in step one, to stir 10min ~ 15min under 2000r/min ~ 2500r/min rotating speed in high-speed mixer, namely complete the preparation of PVC wood plastic composite material composite halogen-free anti-flaming smoke-inhibiting agent.
The method that described employing composite halogen-free anti-flaming smoke-inhibiting agent prepares PVC wood plastic composite material is carried out according to the following steps:
One, in mass ratio: polyvinyl chloride resin: lignocellulosic material: thermo-stabilizer: softening agent: solubilizing agent: lubricant: composite halogen-free anti-flaming smoke-inhibiting agent=100:(30 ~ 80): (4 ~ 12): (3 ~ 20): (5 ~ 10): (0.5 ~ 2): (3 ~ 30) take polyvinyl chloride resin, lignocellulosic material, thermo-stabilizer, softening agent, solvent, lubricant and composite halogen-free anti-flaming smoke-inhibiting agent;
Polyvinyl chloride resin, thermo-stabilizer, softening agent, solubilizing agent, lubricant, composite halogen-free anti-flaming smoke-inhibiting agent are joined successively in high-speed mixer and carry out premix; Rotating speed during described premix in high-speed mixer is 2000r/min ~ 2500r/min, does time as 10min ~ 15min in advance;
Described thermoplastics is polyvinyl chloride (PVC) RESINS or waste vinylene chloride plastic, also can be the mixture of the two; Described lignocellulosic material is the arbitrary proportion mixture of any one or more in wood powder, bamboo powder, agricultural residues powder, shell powder; Described lignocellulosic material particle diameter is 80 order ~ 200 orders; Described thermo-stabilizer is rare earth thermal stabilizer, organo-tin het stabilizer etc., and thermo-stabilizer is mainly in order to improve the thermostability of polyvinyl chloride resin; Described softening agent is dibutyl phthalate (DOP) or dioctyl phthalate (DOP) (DCP), and softening agent is mainly in order to increase the plasticizing capacity of polyvinyl chloride (PVC) RESINS; Described lubricant is stearic acid and metal-salt, paraffin or polyethylene wax; Described increase-volume is maleic anhydride inoculated polypropylene (PP-g-MA), maleic anhydride grafted polyethylene (PE-g-MA), chlorinatedpolyethylene (CPE), titanic acid ester, isocyanic ester or silane coupling agent etc., and solubilizing agent is to increase the interface compatibility between lignocellulosic material and plastics, the mechanical property improving material and processing characteristics;
Two, adjusting high-speed mixer temperature is 80 DEG C ~ 90 DEG C, after 5min ~ 10min, then the lignocellulosic material that step one takes is joined in the high-speed mixer of step one, adjustment high-speed mixer temperature to 90 DEG C ~ 105 DEG C the water ratio being stirred to lignocellulosic material reaches less than 2%, obtains high-temperature material; Wherein, higher temperature is conducive to removing the composition being unfavorable for interface cohesion in lignocellulosic material;
Three, by high-temperature material discharging in step 2 in low speed cold mixer, discharging when material temperature reaches 45 DEG C, obtains Preblend;
Four, Preblend is placed in extrudes unit and extrusion moulding, namely complete the preparation of non-halogen flame-proof smoke-restraining type PVC wood plastic composite material; Described forcing machine is single screw extrusion machine, parallel double-screw Dual inoculation or conical double screw extruder; In described extrusion moulding process, extruder barrel Heating temperature is 135 DEG C ~ 175 DEG C, and die temperature is 160 DEG C ~ 165 DEG C, and can adjust among a small circle according to compound composition point difference;
Due to the one-tenth charcoal effect of wood fibre self, can according to the difference of wood fibre content in compound system, ratio in adjustment composite halogen-free anti-flaming smoke-inhibiting agent between each component, be applied to the PVC wood plastic composite material system of different wood fibre content, reach best cost performance, in described PVC wood plastic composite material, in the proportioning of composite halogen-free anti-flaming smoke-inhibiting agent and PVC wood plastic composite material, the pass of lignocellulosic material mass percentage is: if lignocellulosic material mass percentage is below 40% in PVC wood plastic composite material, then the proportioning of composite halogen-free anti-flaming smoke-inhibiting agent is: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(0.4 ~ 1): (0.3 ~ 1): (0.3 ~ 1): 1, if lignocellulosic material mass percentage is 40 ~ 60% in PVC wood plastic composite material, then the proportioning of composite halogen-free anti-flaming smoke-inhibiting agent is: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(1 ~ 3): (1 ~ 2): (2 ~ 3): 1, if lignocellulosic material mass percentage is greater than 60% in PVC wood plastic composite material, then the proportioning of composite halogen-free anti-flaming smoke-inhibiting agent is: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(3 ~ 4): (2 ~ 3): (2 ~ 3): 1,
In order to meet the application of material in the different occasion of indoor and outdoor, prepare the conventional modified additive that can also add plastic working in wood plastic composite process in right amount at composite halogen-free anti-flaming smoke-inhibiting agent, as oxidation inhibitor, toughner, tinting material etc.
The present invention possesses following beneficial effect:
1, composite halogen-free anti-flaming smoke-inhibiting agent of the present invention, flame-retardant smoke inhibition process is carried out to the main component wood fibre of wood plastic composite and polyvinyl chloride simultaneously, lignocellulosic material doubles as auxiliary char-forming agent in flame-retardant system, flame-retardant smoke inhibition effect has obvious advantage, and addition is few, cost is low.
In the fire retardant systems of 2, composite halogen-free anti-flaming smoke-inhibiting agent of the present invention and in processing aid, do not adopt any halogenated flame retardant, lead salt etc. to environment and the harmful additive of health of people.
3, when composite halogen-free anti-flaming smoke-inhibiting agent of the present invention uses, can according to the changing conditions of lignocellulosic components, adopt different anti-flaming smoke-inhibiting agent component proportion, reach optimum resistance combustion smoke suppressing effect, applied widely, can be applicable to indoor and other occasions that flame retardant properties is had higher requirements, as indoor floor, top ceiling, decoration decorative sheet, sash stuff, office furniture etc., can be used as transportation means inside gadget, electric type shell etc. in addition.And the advantage that the flame-retarding smoke-inhibiting PVC wood plastic matrix material adopting the inventive method to prepare has a normal wood plastic composite materials as material appearance be similar to timber, have woodiness touch, good visual effect, have the premium properties of timber and thermoplastics concurrently.Can saw, can dig, can follow closely, good processability, be easy to install, Anti-moth-eating, corrosion-resistant, moisture resistance, anti-skidding, good stability of the dimension.
4, the resistance to burning time of composite halogen-free anti-flaming smoke-inhibiting agent of the present invention to material changes not obvious, can ensure the machining property impact of material little simultaneously.
5, the interaction in composite halogen-free anti-flaming smoke-inhibiting agent of the present invention between intumescent system and cupric oxide and wood fibre, PVC, after adding anti-flaming smoke-inhibiting agent of the present invention, obvious black smoke is not produced during matrix material burning, cigarette output obviously reduces simultaneously, and this is favourable to the fire hazard of reduction material.This composite flame-retardant agent not only gives wood plastic composite good flame retardant resistance, and smoke suppressing is excellent, and usage quantity is few, is therefore applicable PVC wood plastic system, has fire-retardant and but the composite halogen-free anti-flaming smoke-inhibiting agent of cigarette double effects.
According to ISO5660-1, adopt the PVC wood plastic composite material that the present invention produces, its fire-retardant and smoke suppressing significantly improves.Cohesion due to wood fibre and Intumscent Flame Retardant System is coordinated charcoal effect, and cupric oxide is to polyvinyl chloride resin in combustion to the promoter action of degraded dehydrochlorination in addition, and the neat coal amout of wood fibre and PVC system is obviously increased.
According to GB/T2406.2-2009, the oxygen index of most of wood plastic composite is 16% ~ 20%, and the flame-proof PVC wood plastic composite oxygen index adopting composite halogen-free anti-flaming smoke-inhibiting agent of the present invention to prepare, more than 35% ~ 41%, belongs to difficult combustion level material.
Tapered calorimeter experimental result shows, when wood fibre content is 30%, add the PVC wood plastic composite material after composite flame-retardant agent of the present invention 5 parts (weight), in combustion processes, total heat release rate reduces by 27.0%, and smoke-producing amount reduction by 41.7%, carbon dioxide produce improve 3.9%.In addition, adopt wood plastic composite prepared by anti-flaming smoke-inhibiting agent of the present invention, during burning, its oxygen index reaches 41%, and burning time is long, does not melt and drips; When wood powder content is 70%, add the PVC wood plastic composite material after composite flame-retardant agent of the present invention 3 parts (weight), in combustion processes, total Thermal release rate reduces by 29%, and total smoke-producing amount reduction by 57%, carbon dioxide produce improve 15%; PVC wood plastic composite material after adding composite flame-retardant agent of the present invention 5 parts (weight), in combustion processes, total Thermal release rate reduces by 15%, and total smoke-producing amount reduction by 45%, carbon dioxide produce improve 7.8%, show excellent smoke suppressing.
6, a kind of flame-retarding smoke-inhibiting PVC wood plastic matrix material of preparing of the present invention, compared with existing PVC wood plastic composite material, have fire retardant and add few, flame-retardant smoke inhibition efficiency is high.Meanwhile, can ensure to affect little on the machining property of material.
Embodiment
Embodiment one: the composite halogen-free anti-flaming smoke-inhibiting agent of a kind of PVC wood plastic composite material of present embodiment, this composite halogen-free anti-flaming smoke-inhibiting agent is made up of polyphosphoric acid amine, trimeric cyanamide, tetramethylolmethane and cupric oxide, is in mass ratio: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide composition=(0.4 ~ 4): (0.3 ~ 3): (0.3 ~ 3): 1; The polymerization degree n > 1500 of described ammonium polyphosphate.
Present embodiment possesses following beneficial effect:
1, the composite halogen-free anti-flaming smoke-inhibiting agent of present embodiment, flame-retardant smoke inhibition process is carried out to the main component wood fibre of wood plastic composite and polyvinyl chloride simultaneously, lignocellulosic material doubles as auxiliary char-forming agent in flame-retardant system, flame-retardant smoke inhibition effect has obvious advantage, and addition is few, cost is low.
In the fire retardant systems of 2, the composite halogen-free anti-flaming smoke-inhibiting agent of present embodiment and in processing aid, do not adopt any halogenated flame retardant, lead salt etc. to environment and the harmful additive of health of people.
3, when the composite halogen-free anti-flaming smoke-inhibiting agent of present embodiment uses, can according to the changing conditions of lignocellulosic components, adopt different anti-flaming smoke-inhibiting agent component proportion, reach optimum resistance combustion smoke suppressing effect, applied widely, can be applicable to indoor and other occasions that flame retardant properties is had higher requirements, as indoor floor, top ceiling, decoration decorative sheet, sash stuff, office furniture etc., can be used as transportation means inside gadget, electric type shell etc. in addition.And the advantage that the flame-retarding smoke-inhibiting PVC wood plastic matrix material adopting present embodiment method to prepare has a normal wood plastic composite materials as material appearance be similar to timber, have woodiness touch, good visual effect, have the premium properties of timber and thermoplastics concurrently.Can saw, can dig, can follow closely, good processability, be easy to install, Anti-moth-eating, corrosion-resistant, moisture resistance, anti-skidding, good stability of the dimension.
4, the resistance to burning time of present embodiment composite halogen-free anti-flaming smoke-inhibiting agent to material changes not obvious, can ensure the machining property impact of material little simultaneously.
5, the interaction in present embodiment composite halogen-free anti-flaming smoke-inhibiting agent between intumescent system and cupric oxide and wood fibre, PVC, after adding the anti-flaming smoke-inhibiting agent of present embodiment, obvious black smoke is not produced during matrix material burning, cigarette output obviously reduces simultaneously, and this is favourable to the fire hazard of reduction material.This composite flame-retardant agent not only gives wood plastic composite good flame retardant resistance, and smoke suppressing is excellent, and usage quantity is few, is therefore applicable PVC wood plastic system, has fire-retardant and but the composite halogen-free anti-flaming smoke-inhibiting agent of cigarette double effects.
According to ISO5660-1, adopt the PVC wood plastic composite material that present embodiment is produced, its fire-retardant and smoke suppressing significantly improves.Cohesion due to wood fibre and Intumscent Flame Retardant System is coordinated charcoal effect, and cupric oxide is to polyvinyl chloride resin in combustion to the promoter action of degraded dehydrochlorination in addition, and the neat coal amout of wood fibre and PVC system is obviously increased.
According to GB/T2406.2-2009, the oxygen index of most of wood plastic composite is 16% ~ 20%, and flame-proof PVC wood plastic composite oxygen index prepared by employing present embodiment composite halogen-free anti-flaming smoke-inhibiting agent, more than 35% ~ 41%, belongs to difficult combustion level material.
Tapered calorimeter experimental result shows, when wood fibre content is 30%, add the PVC wood plastic composite material after the composite flame-retardant agent 5 parts (weight) of present embodiment, in combustion processes, total heat release rate reduces by 27.0%, and smoke-producing amount reduction by 41.7%, carbon dioxide produce improve 3.9%.In addition, adopt wood plastic composite prepared by present embodiment anti-flaming smoke-inhibiting agent, during burning, its oxygen index reaches 41%, and burning time is long, does not melt and drips; When wood powder content is 70%, add the PVC wood plastic composite material after the composite flame-retardant agent 3 parts (weight) of present embodiment, in combustion processes, total Thermal release rate reduces by 29%, and total smoke-producing amount reduction by 57%, carbon dioxide produce improve 15%; PVC wood plastic composite material after the composite flame-retardant agent 5 parts (weight) adding present embodiment, in combustion processes, total Thermal release rate reduces by 15%, and total smoke-producing amount reduction by 45%, carbon dioxide produce improve 7.8%, show excellent smoke suppressing.
6, a kind of flame-retarding smoke-inhibiting PVC wood plastic matrix material of preparing of present embodiment, compared with existing PVC wood plastic composite material, have fire retardant and add few, flame-retardant smoke inhibition efficiency is high.Meanwhile, can ensure to affect little on the machining property of material.
Embodiment two: present embodiment and embodiment one are unlike the polymerization degree n > 1500 of described ammonium polyphosphate.Other step is identical with embodiment one with parameter.
Embodiment three: a kind of method preparing the composite halogen-free anti-flaming smoke-inhibiting agent of PVC wood plastic composite material of present embodiment, the method is carried out according to the following steps:
One, be in mass ratio: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(0.4 ~ 4): (0.3 ~ 3): (0.3 ~ 3): 1 takes polyphosphoric acid amine, trimeric cyanamide, tetramethylolmethane and cupric oxide as raw material, the polyphosphoric acid amine, trimeric cyanamide and the tetramethylolmethane that take are placed in high-speed mixer, under 2000r/min ~ 2500r/min rotating speed, stir 10min ~ 15min, namely complete the preparation of expansion type flame retardant;
Two, cupric oxide step one taken is as fire retarding synergist, join in the expansion type flame retardant of preparation in step one, to stir 10min ~ 15min under 2000r/min ~ 2500r/min rotating speed in high-speed mixer, namely complete the preparation of PVC wood plastic composite material composite halogen-free anti-flaming smoke-inhibiting agent.
Present embodiment possesses following beneficial effect:
1, the composite halogen-free anti-flaming smoke-inhibiting agent of present embodiment, flame-retardant smoke inhibition process is carried out to the main component wood fibre of wood plastic composite and polyvinyl chloride simultaneously, lignocellulosic material doubles as auxiliary char-forming agent in flame-retardant system, flame-retardant smoke inhibition effect has obvious advantage, and addition is few, cost is low.
In the fire retardant systems of 2, the composite halogen-free anti-flaming smoke-inhibiting agent of present embodiment and in processing aid, do not adopt any halogenated flame retardant, lead salt etc. to environment and the harmful additive of health of people.
3, when the composite halogen-free anti-flaming smoke-inhibiting agent of present embodiment uses, can according to the changing conditions of lignocellulosic components, adopt different anti-flaming smoke-inhibiting agent component proportion, reach optimum resistance combustion smoke suppressing effect, applied widely, can be applicable to indoor and other occasions that flame retardant properties is had higher requirements, as indoor floor, top ceiling, decoration decorative sheet, sash stuff, office furniture etc., can be used as transportation means inside gadget, electric type shell etc. in addition.And the advantage that the flame-retarding smoke-inhibiting PVC wood plastic matrix material adopting present embodiment method to prepare has a normal wood plastic composite materials as material appearance be similar to timber, have woodiness touch, good visual effect, have the premium properties of timber and thermoplastics concurrently.Can saw, can dig, can follow closely, good processability, be easy to install, Anti-moth-eating, corrosion-resistant, moisture resistance, anti-skidding, good stability of the dimension.
4, the resistance to burning time of present embodiment composite halogen-free anti-flaming smoke-inhibiting agent to material changes not obvious, can ensure the machining property impact of material little simultaneously.
5, the interaction in present embodiment composite halogen-free anti-flaming smoke-inhibiting agent between intumescent system and cupric oxide and wood fibre, PVC, after adding the anti-flaming smoke-inhibiting agent of present embodiment, obvious black smoke is not produced during matrix material burning, cigarette output obviously reduces simultaneously, and this is favourable to the fire hazard of reduction material.This composite flame-retardant agent not only gives wood plastic composite good flame retardant resistance, and smoke suppressing is excellent, and usage quantity is few, is therefore applicable PVC wood plastic system, has fire-retardant and but the composite halogen-free anti-flaming smoke-inhibiting agent of cigarette double effects.
According to ISO5660-1, adopt the PVC wood plastic composite material that present embodiment is produced, its fire-retardant and smoke suppressing significantly improves.Cohesion due to wood fibre and Intumscent Flame Retardant System is coordinated charcoal effect, and cupric oxide is to polyvinyl chloride resin in combustion to the promoter action of degraded dehydrochlorination in addition, and the neat coal amout of wood fibre and PVC system is obviously increased.
According to GB/T2406.2-2009, the oxygen index of most of wood plastic composite is 16% ~ 20%, and flame-proof PVC wood plastic composite oxygen index prepared by employing present embodiment composite halogen-free anti-flaming smoke-inhibiting agent, more than 35% ~ 41%, belongs to difficult combustion level material.
Tapered calorimeter experimental result shows, when wood fibre content is 30%, add the PVC wood plastic composite material after the composite flame-retardant agent 5 parts (weight) of present embodiment, in combustion processes, total heat release rate reduces by 27.0%, and smoke-producing amount reduction by 41.7%, carbon dioxide produce improve 3.9%.In addition, adopt wood plastic composite prepared by present embodiment anti-flaming smoke-inhibiting agent, during burning, its oxygen index reaches 41%, and burning time is long, does not melt and drips; When wood powder content is 70%, add the PVC wood plastic composite material after the composite flame-retardant agent 3 parts (weight) of present embodiment, in combustion processes, total Thermal release rate reduces by 29%, and total smoke-producing amount reduction by 57%, carbon dioxide produce improve 15%; PVC wood plastic composite material after the composite flame-retardant agent 5 parts (weight) adding present embodiment, in combustion processes, total Thermal release rate reduces by 15%, and total smoke-producing amount reduction by 45%, carbon dioxide produce improve 7.8%, show excellent smoke suppressing.
6, a kind of flame-retarding smoke-inhibiting PVC wood plastic matrix material of preparing of present embodiment, compared with existing PVC wood plastic composite material, have fire retardant and add few, flame-retardant smoke inhibition efficiency is high.Meanwhile, can ensure to affect little on the machining property of material.
Embodiment three: present embodiment adopts composite halogen-free anti-flaming smoke-inhibiting agent to prepare the method for PVC wood plastic composite material, and the method is carried out according to the following steps:
One, in mass ratio: polyvinyl chloride resin: lignocellulosic material: thermo-stabilizer: softening agent: solubilizing agent: lubricant: composite halogen-free anti-flaming smoke-inhibiting agent=100:(30 ~ 80): (4 ~ 12): (3 ~ 20): (5 ~ 10): (0.5 ~ 2): (3 ~ 30) take polyvinyl chloride resin, lignocellulosic material, thermo-stabilizer, softening agent, solvent, lubricant and composite halogen-free anti-flaming smoke-inhibiting agent;
Polyvinyl chloride resin, thermo-stabilizer, softening agent, solubilizing agent, lubricant, composite halogen-free anti-flaming smoke-inhibiting agent are joined successively in high-speed mixer and carry out premix; Rotating speed during described premix in high-speed mixer is 2000r/min ~ 2500r/min, does time as 10min ~ 15min in advance;
Two, adjusting high-speed mixer temperature is 80 DEG C ~ 90 DEG C, after 5min ~ 10min, then the lignocellulosic material that step one takes is joined in the high-speed mixer of step one, adjustment high-speed mixer temperature to 90 DEG C ~ 105 DEG C the water ratio being stirred to lignocellulosic material reaches less than 2%, obtains high-temperature material;
Three, by high-temperature material discharging in step 2 in low speed cold mixer, discharging when material temperature reaches 45 DEG C, obtains Preblend;
Four, Preblend is placed in extrudes unit and extrusion moulding, namely complete the preparation of non-halogen flame-proof smoke-restraining type PVC wood plastic composite material; Described forcing machine is single screw extrusion machine, parallel double-screw Dual inoculation or conical double screw extruder; In described extrusion moulding process, extruder barrel Heating temperature is 135 DEG C ~ 175 DEG C, and die temperature is 160 DEG C ~ 165 DEG C;
Due to the one-tenth charcoal effect of wood fibre self, can according to the difference of lignocellulosic material content in PVC wood plastic composite material, ratio in adjustment composite halogen-free anti-flaming smoke-inhibiting agent between each component, be applied to the PVC wood plastic composite material system of different wood fibre content, reach best cost performance, in described PVC wood plastic composite material, in the proportioning of composite halogen-free anti-flaming smoke-inhibiting agent and PVC wood plastic composite material, the pass of lignocellulosic material mass percentage is: if lignocellulosic material mass percentage is below 40% in PVC wood plastic composite material, then the proportioning of composite halogen-free anti-flaming smoke-inhibiting agent is: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(0.4 ~ 1): (0.3 ~ 1): (0.3 ~ 1): 1, if lignocellulosic material mass percentage is 40 ~ 60% in PVC wood plastic composite material, then the proportioning of composite halogen-free anti-flaming smoke-inhibiting agent is: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(1 ~ 3): (1 ~ 2): (2 ~ 3): 1, if lignocellulosic material mass percentage is greater than 60% in PVC wood plastic composite material, then the proportioning of composite halogen-free anti-flaming smoke-inhibiting agent is: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(3 ~ 4): (2 ~ 3): (2 ~ 3): 1.
Present embodiment possesses following beneficial effect:
1, the composite halogen-free anti-flaming smoke-inhibiting agent of present embodiment, flame-retardant smoke inhibition process is carried out to the main component wood fibre of wood plastic composite and polyvinyl chloride simultaneously, lignocellulosic material doubles as auxiliary char-forming agent in flame-retardant system, flame-retardant smoke inhibition effect has obvious advantage, and addition is few, cost is low.
In the fire retardant systems of 2, the composite halogen-free anti-flaming smoke-inhibiting agent of present embodiment and in processing aid, do not adopt any halogenated flame retardant, lead salt etc. to environment and the harmful additive of health of people.
3, when the composite halogen-free anti-flaming smoke-inhibiting agent of present embodiment uses, can according to the changing conditions of lignocellulosic components, adopt different anti-flaming smoke-inhibiting agent component proportion, reach optimum resistance combustion smoke suppressing effect, applied widely, can be applicable to indoor and other occasions that flame retardant properties is had higher requirements, as indoor floor, top ceiling, decoration decorative sheet, sash stuff, office furniture etc., can be used as transportation means inside gadget, electric type shell etc. in addition.And the advantage that the flame-retarding smoke-inhibiting PVC wood plastic matrix material adopting present embodiment method to prepare has a normal wood plastic composite materials as material appearance be similar to timber, have woodiness touch, good visual effect, have the premium properties of timber and thermoplastics concurrently.Can saw, can dig, can follow closely, good processability, be easy to install, Anti-moth-eating, corrosion-resistant, moisture resistance, anti-skidding, good stability of the dimension.
4, the resistance to burning time of present embodiment composite halogen-free anti-flaming smoke-inhibiting agent to material changes not obvious, can ensure the machining property impact of material little simultaneously.
5, the interaction in present embodiment composite halogen-free anti-flaming smoke-inhibiting agent between intumescent system and cupric oxide and wood fibre, PVC, after adding the anti-flaming smoke-inhibiting agent of present embodiment, obvious black smoke is not produced during matrix material burning, cigarette output obviously reduces simultaneously, and this is favourable to the fire hazard of reduction material.This composite flame-retardant agent not only gives wood plastic composite good flame retardant resistance, and smoke suppressing is excellent, and usage quantity is few, is therefore applicable PVC wood plastic system, has fire-retardant and but the composite halogen-free anti-flaming smoke-inhibiting agent of cigarette double effects.
According to ISO5660-1, adopt the PVC wood plastic composite material that present embodiment is produced, its fire-retardant and smoke suppressing significantly improves.Cohesion due to wood fibre and Intumscent Flame Retardant System is coordinated charcoal effect, and cupric oxide is to polyvinyl chloride resin in combustion to the promoter action of degraded dehydrochlorination in addition, and the neat coal amout of wood fibre and PVC system is obviously increased.
According to GB/T2406.2-2009, the oxygen index of most of wood plastic composite is 16% ~ 20%, and flame-proof PVC wood plastic composite oxygen index prepared by employing present embodiment composite halogen-free anti-flaming smoke-inhibiting agent, more than 35% ~ 41%, belongs to difficult combustion level material.
Tapered calorimeter experimental result shows, when wood fibre content is 30%, add the PVC wood plastic composite material after the composite flame-retardant agent 5 parts (weight) of present embodiment, in combustion processes, total heat release rate reduces by 27.0%, and smoke-producing amount reduction by 41.7%, carbon dioxide produce improve 3.9%.In addition, adopt wood plastic composite prepared by present embodiment anti-flaming smoke-inhibiting agent, during burning, its oxygen index reaches 41%, and burning time is long, does not melt and drips; When wood powder content is 70%, add the PVC wood plastic composite material after the composite flame-retardant agent 3 parts (weight) of present embodiment, in combustion processes, total Thermal release rate reduces by 29%, and total smoke-producing amount reduction by 57%, carbon dioxide produce improve 15%; PVC wood plastic composite material after the composite flame-retardant agent 5 parts (weight) adding present embodiment, in combustion processes, total Thermal release rate reduces by 15%, and total smoke-producing amount reduction by 45%, carbon dioxide produce improve 7.8%, show excellent smoke suppressing.
6, a kind of flame-retarding smoke-inhibiting PVC wood plastic matrix material of preparing of present embodiment, compared with existing PVC wood plastic composite material, have fire retardant and add few, flame-retardant smoke inhibition efficiency is high.Meanwhile, can ensure to affect little on the machining property of material.
Embodiment four: present embodiment and embodiment three unlike: in step one.Described thermoplastics is polyvinyl chloride (PVC) RESINS or waste vinylene chloride plastic, also can be the mixture of the two.Other step is identical with embodiment three with parameter.
Embodiment five: present embodiment and embodiment three or four unlike: lignocellulosic material described in step one is the arbitrary proportion mixture of any one or more in wood powder, bamboo powder, agricultural residues powder, shell powder; Described lignocellulosic material particle diameter is 80 order ~ 200 orders.Other step is identical with embodiment three or four with parameter.
Embodiment six: one of present embodiment and embodiment three to five unlike: thermo-stabilizer described in step one is rare earth thermal stabilizer, organo-tin het stabilizer.Other step is identical with one of parameter and embodiment three to five.
Embodiment seven: one of present embodiment and embodiment three to six unlike: softening agent described in step one is dibutyl phthalate (DOP) or dioctyl phthalate (DOP) (DCP).Other step is identical with one of parameter and embodiment three to six.
Embodiment eight: one of present embodiment and embodiment three to seven unlike: lubricant described in step one is stearic acid and metal-salt, paraffin or polyethylene wax.Other step is identical with one of parameter and embodiment three to seven.
Embodiment nine: one of present embodiment and embodiment three to eight unlike: increase-volume described in step one is maleic anhydride inoculated polypropylene (PP-g-MA), maleic anhydride grafted polyethylene (PE-g-MA), chlorinatedpolyethylene (CPE), titanic acid ester, isocyanic ester or silane coupling agent.Other step is identical with one of parameter and embodiment three to eight.
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
The preparation method of described PVC wood plastic composite material composite halogen-free anti-flaming smoke-inhibiting agent carries out according to the following steps:
One, be in mass ratio: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=0.4:0.3:0.3:1 takes polyphosphoric acid amine, trimeric cyanamide, tetramethylolmethane and cupric oxide as raw material, the polyphosphoric acid amine, trimeric cyanamide and the tetramethylolmethane that take are placed in high-speed mixer, under 2500r/min rotating speed, stir 15min, namely complete the preparation of expansion type flame retardant; The polymerization degree n > 1500 of described ammonium polyphosphate;
Two, cupric oxide step one taken is as fire retarding synergist, join in the expansion type flame retardant of preparation in step one, to stir 15min under 2500r/min rotating speed in high-speed mixer, namely complete the preparation of PVC wood plastic composite material composite halogen-free anti-flaming smoke-inhibiting agent.
Embodiment 2
The composite halogen-free anti-flaming smoke-inhibiting agent of the present embodiment employing prepared by embodiment 1 is prepared flame-retarding smoke-inhibiting PVC wood plastic matrix material and is carried out according to the following steps:
One, in mass ratio: polyvinyl chloride resin: lignocellulosic material: thermo-stabilizer: softening agent: solubilizing agent: lubricant: composite halogen-free anti-flaming smoke-inhibiting agent=301:150:18:15:15:1:30 takes polyvinyl chloride resin, lignocellulosic material, thermo-stabilizer, softening agent, solvent, lubricant and composite halogen-free anti-flaming smoke-inhibiting agent; Polyvinyl chloride resin, thermo-stabilizer, softening agent, solubilizing agent, lubricant, composite halogen-free anti-flaming smoke-inhibiting agent are joined successively in high-speed mixer and carry out premix; Rotating speed during described premix in high-speed mixer is 2000r/min, does time as 10min in advance;
Two, adjusting high-speed mixer temperature is 80 DEG C, after 10min, then the lignocellulosic material that step one takes is joined in the high-speed mixer of step one, adjustment high-speed mixer temperature to 90 DEG C the water ratio being stirred to lignocellulosic material reaches less than 2%, obtain high-temperature material; Wherein, higher temperature is conducive to removing the composition being unfavorable for interface cohesion in lignocellulosic material;
Three, by high-temperature material discharging in step 2 in low speed cold mixer, discharging when material temperature reaches 45 DEG C, obtains Preblend;
Four, Preblend is placed in extrudes unit and extrusion moulding, namely complete the preparation of flame-retarding smoke-inhibiting PVC wood plastic matrix material;
In described extrusion moulding process, extruder barrel Heating temperature is 135 DEG C, and die temperature is 160 DEG C; Described forcing machine is single screw extrusion machine; Described thermoplastics is polyvinyl chloride (PVC) RESINS; Described lignocellulosic material is the arbitrary proportion mixture of any one or more in wood powder, bamboo powder, agricultural residues powder, shell powder; Described wood powder particle diameter is 150 orders; Described thermo-stabilizer is organo-tin het stabilizer; Described softening agent is dibutyl phthalate (DOP); Described lubricant is polyethylene wax; Described increase-volume is maleic anhydride inoculated polypropylene (PP-g-MA); Described lubricant is paraffin;
The main ingredient ratio of the preparation of flame-retarding smoke-inhibiting PVC wood plastic matrix material prepared by the present embodiment is as shown in sample in table 12, and wherein sample 1 is the control group formula not adding composite halogen-free flame-retardant smoke inhibition.
In the present embodiment, the processing parameter of 2 groups of experiments remains unchanged.In experimentation, the present embodiment extruded product is the sheet material of the wide 40mm of sectional dimension and thick 4mm, and the sheet material extruded is processed into standard specimen, carries out oxygen index and cone calorimetry (hot-fluid 50kW/m
2) simultaneous test, with its fire-retardant and smoke suppressing of system evaluation, the results are shown in Table 2, sample 2 is flame-retarding smoke-inhibiting PVC wood plastic matrix material, and sample 1 is the control group formula not adding composite halogen-free flame-retardant smoke inhibition.
When testing for oxygen index, the sheet material extruded directly is cut into the geomery that testing method requires.When testing for combustionproperty, by sheet material laterally parallel splicing be pressed into the thin plate of thickness 4.0mm on thermocompressor, then cut into the sample being of a size of 100mm × 100mm and be used for CONE test.Oxygen index test is according to GB/T2406-2009 standard; Flame retardant properties test is according to ISO5660-1 standard.
Test result shows: with do not add compared with fire retardant processing sample 1, sample 2 can slow down total heat release during composite wood burning effectively, suppresses fire propagate and spread.Wherein total cigarette output of sample 2 is compared with untreated samples 1, and fire-retardant finish makes the obviously reduction by 52.2% of sample unit surface cigarette output; Total heat release reduces by 19.98%, and burns oxygen index is increased to 41% from 35.2.It is little that Halogen composite halogen-free anti-flaming smoke-inhibiting agent of the present invention has consumption, has fire-retardant and smoke suppressing effect significantly to wood powder/PVC matrix material.
The main ingredient ratio of wood plastic composite in table 1 embodiment 1
Wood plastic composite flame retarding and smoke suppressing properties test in table 2 embodiment 1
Embodiment 3
In the present embodiment material basic components in the weight fraction ratio of each component be polyvinyl chloride: thermo-stabilizer: MAPP:DOP=100:6:5:5, composite halogen-free anti-flaming smoke-inhibiting agent is made up of polyphosphoric acid amine, trimeric cyanamide, tetramethylolmethane and cupric oxide, and mass ratio is: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=24:17:11:50; Prepare the flame-retarding smoke-inhibiting PVC wood plastic matrix material that five kinds of wood powder contents are 30% in the present embodiment, the consumption of anti-flaming smoke-inhibiting agent is as shown in table 3, and other raw materials are identical with embodiment 2 with technique; In the present embodiment, the combustionproperty of PVC wood plastic composite material is as shown in table 4;
Test result shows: when wood powder content is 30%, along with cupric oxide consumption in fire retardant reduces, in expanding fire retardant, ammonium polyphosphate consumption increases, compared with the sample 1 not adding fire retardant, sample 2,3,4,5 combustion processes total smoke release reduces by 13.79%, 26.79%, 17.32%, 44.07% respectively, and total burst size reduces by 10.99% ~ 45.39%.Smoke toxicity index carbon monoxide yields also has and reduces in various degree, and the carbon left of sample obviously increases.When wood powder content is identical, composite flame-retardant agent consumption by 5% increase time to 20% time, total smoke release and total heat release reduce by 32.35% and 39.28% respectively.Therefore, the PVC wood plastic composite material for low wood powder content is passed through under basic maintenance trimeric cyanamide and tetramethylolmethane consumption situation, and the consumption of adjustment cupric oxide reaches obvious flame-retardant smoke inhibition effect.
Composite halogen-free anti-flaming smoke-inhibiting agent component proportion and consumption in table 3 embodiment 2
The combustionproperty of PVC wood plastic composite material in table 4 embodiment 2
Embodiment 4
In the present embodiment, the basic components of material is with embodiment 2, adopt in the present embodiment three kinds of wood powder contents be 70% PVC wood plastic composite material carry out cone calorimetry combustion experiment, the consumption of anti-flaming smoke-inhibiting agent is as shown in table 5, other raw materials are identical with embodiment 3 with technique, and in the present embodiment, the combustionproperty of PVC wood plastic composite material is as shown in table 6;
Test result shows: when wood powder content reaches 70%, and when using the composite flame-retardant agent of 3%, along with in fire retardant, cupric oxide consumption is increased to 50% by 9%, and in material combustion process, total heat release reduces by 17.43%, and total smoke release reduces by 19.56%.When composite flame-retardant agent consumption is increased to 5% by 3%, corresponding total smoke release increases by 3.6%, and the smoke toxicity of products of combustion and carbon left increase.PVC matrix material for high wood powder content is described, increase cupric oxide consumption, smoke suppressing effect is obvious.
Composite halogen-free anti-flaming smoke-inhibiting agent component proportion and consumption in table 5 embodiment 3
The combustionproperty of PVC wood plastic composite material in table 6 embodiment 3
Claims (10)
1. the composite halogen-free anti-flaming smoke-inhibiting agent of a PVC wood plastic composite material, it is characterized in that this composite halogen-free anti-flaming smoke-inhibiting agent is made up of polyphosphoric acid amine, trimeric cyanamide, tetramethylolmethane and cupric oxide, be in mass ratio: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(0.4 ~ 4): (0.3 ~ 3): (0.3 ~ 3): 1.
2. the composite halogen-free anti-flaming smoke-inhibiting agent of a kind of PVC wood plastic composite material according to claim 1, is characterized in that the polymerization degree n > 1500 of described ammonium polyphosphate.
3. prepare a method for the composite halogen-free anti-flaming smoke-inhibiting agent of PVC wood plastic composite material as claimed in claim 1, it is characterized in that the method is carried out according to the following steps:
One, be in mass ratio: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(0.4 ~ 4): (0.3 ~ 3): (0.3 ~ 3): 1 takes polyphosphoric acid amine, trimeric cyanamide, tetramethylolmethane and cupric oxide as raw material, the polyphosphoric acid amine, trimeric cyanamide and the tetramethylolmethane that take are placed in high-speed mixer, under 2000r/min ~ 2500r/min rotating speed, stir 10min ~ 15min, namely complete the preparation of expansion type flame retardant;
Two, cupric oxide step one taken is as fire retarding synergist, join in the expansion type flame retardant of preparation in step one, to stir 10min ~ 15min under 2000r/min ~ 2500r/min rotating speed in high-speed mixer, namely complete the preparation of PVC wood plastic composite material composite halogen-free anti-flaming smoke-inhibiting agent.
4. the application of composite halogen-free anti-flaming smoke-inhibiting agent as claimed in claim 1, it is characterized in that adopting composite halogen-free anti-flaming smoke-inhibiting agent to prepare PVC wood plastic composite material, concrete grammar is:
One, in mass ratio: polyvinyl chloride resin: lignocellulosic material: thermo-stabilizer: softening agent: solubilizing agent: lubricant: composite halogen-free anti-flaming smoke-inhibiting agent=100:(30 ~ 80): (4 ~ 12): (3 ~ 20): (5 ~ 10): (0.5 ~ 2): (3 ~ 30) take polyvinyl chloride resin, lignocellulosic material, thermo-stabilizer, softening agent, solvent, lubricant and composite halogen-free anti-flaming smoke-inhibiting agent;
Polyvinyl chloride resin, thermo-stabilizer, softening agent, solubilizing agent, lubricant, composite halogen-free anti-flaming smoke-inhibiting agent are joined successively in high-speed mixer and carry out premix; Rotating speed during described premix in high-speed mixer is 2000r/min ~ 2500r/min, does time as 10min ~ 15min in advance;
Two, adjusting high-speed mixer temperature is 80 DEG C ~ 90 DEG C, after 5min ~ 10min, then the lignocellulosic material that step one takes is joined in the high-speed mixer of step one, adjustment high-speed mixer temperature to 90 DEG C ~ 105 DEG C the water ratio being stirred to lignocellulosic material reaches less than 2%, obtains high-temperature material;
Three, by high-temperature material discharging in step 2 in low speed cold mixer, discharging when material temperature reaches 45 DEG C, obtains Preblend;
Four, Preblend is placed in extrudes unit and extrusion moulding, namely complete the preparation of non-halogen flame-proof smoke-restraining type PVC wood plastic composite material; Described forcing machine is single screw extrusion machine, parallel double-screw Dual inoculation or conical double screw extruder; In described extrusion moulding process, extruder barrel Heating temperature is 135 DEG C ~ 175 DEG C, and die temperature is 160 DEG C ~ 165 DEG C;
In described PVC wood plastic composite material, in the proportioning of composite halogen-free anti-flaming smoke-inhibiting agent and PVC wood plastic composite material, the pass of lignocellulosic material mass percentage is:
If lignocellulosic material mass percentage is below 40% in PVC wood plastic composite material, then the proportioning of composite halogen-free anti-flaming smoke-inhibiting agent is: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(0.4 ~ 1): (0.3 ~ 1): (0.3 ~ 1): 1; If lignocellulosic material mass percentage is 40 ~ 60% in PVC wood plastic composite material, then the proportioning of composite halogen-free anti-flaming smoke-inhibiting agent is: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(1 ~ 3): (1 ~ 2): (2 ~ 3): 1; If lignocellulosic material mass percentage is greater than 60% in PVC wood plastic composite material, then the proportioning of composite halogen-free anti-flaming smoke-inhibiting agent is: polyphosphoric acid amine: trimeric cyanamide: tetramethylolmethane: cupric oxide=(3 ~ 4): (2 ~ 3): (2 ~ 3): 1.
5. employing composite halogen-free anti-flaming smoke-inhibiting agent according to claim 4 prepares the method for PVC wood plastic composite material, it is characterized in that thermoplastics described in step one is polyvinyl chloride (PVC) RESINS or waste vinylene chloride plastic, or the mixture of the two.
6. employing composite halogen-free anti-flaming smoke-inhibiting agent according to claim 4 prepares the method for PVC wood plastic composite material, it is characterized in that lignocellulosic material described in step one is the arbitrary proportion mixture of any one or more in wood powder, bamboo powder, agricultural residues powder, shell powder; Described lignocellulosic material particle diameter is 80 order ~ 200 orders.
7. employing composite halogen-free anti-flaming smoke-inhibiting agent according to claim 4 prepares the method for PVC wood plastic composite material, it is characterized in that thermo-stabilizer described in step one is rare earth thermal stabilizer or organo-tin het stabilizer.
8. employing composite halogen-free anti-flaming smoke-inhibiting agent according to claim 4 prepares the method for PVC wood plastic composite material, it is characterized in that softening agent described in step one is dibutyl phthalate DOP or dioctyl phthalate (DOP) DCP.
9. employing composite halogen-free anti-flaming smoke-inhibiting agent according to claim 4 prepares the method for PVC wood plastic composite material, it is characterized in that lubricant described in step one is stearic acid and metal-salt, paraffin or polyethylene wax.
10. employing composite halogen-free anti-flaming smoke-inhibiting agent according to claim 4 prepares the method for PVC wood plastic composite material, it is characterized in that increase-volume described in step one is maleic anhydride inoculated polypropylene PP-g-MA, maleic anhydride grafted polyethylene PE-g-MA, chlorinatedpolyethylene CPE, titanic acid ester, isocyanic ester or silane coupling agent.
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| CN105924948A (en) * | 2016-07-12 | 2016-09-07 | 广西南宁桂尔创环保科技有限公司 | Novel plastic material |
| CN112694688A (en) * | 2020-12-23 | 2021-04-23 | 台州市黄岩吉通塑管有限公司 | Environment-friendly flame-retardant smoke-suppression type PVC-U material for electrical casing |
| CN116656005A (en) * | 2023-07-28 | 2023-08-29 | 江苏三旌科技材料有限公司 | Composite flame retardant and polymer composite foam material |
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| TWI829383B (en) * | 2022-10-07 | 2024-01-11 | 南亞塑膠工業股份有限公司 | Composition of high flame-retardant and low-smoke polyvinyl chloride extruded pipe and manufacutring method thereof |
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| TWI828356B (en) * | 2022-10-07 | 2024-01-01 | 南亞塑膠工業股份有限公司 | Composition of high flame-retardant and low-smoke polyvinyl chloride injection molding pipe fittings and manufacutring method thereof |
| TWI829383B (en) * | 2022-10-07 | 2024-01-11 | 南亞塑膠工業股份有限公司 | Composition of high flame-retardant and low-smoke polyvinyl chloride extruded pipe and manufacutring method thereof |
| CN116656005A (en) * | 2023-07-28 | 2023-08-29 | 江苏三旌科技材料有限公司 | Composite flame retardant and polymer composite foam material |
| CN116656005B (en) * | 2023-07-28 | 2023-11-21 | 江苏三旌科技材料有限公司 | Composite flame retardant and polymer composite foam material |
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