CN102675776A - High-fluidity high-fire resistance polyvinyl chloride composite material and method for preparing same - Google Patents
High-fluidity high-fire resistance polyvinyl chloride composite material and method for preparing same Download PDFInfo
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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Abstract
The invention discloses a high-fluidity high-fire resistance polyvinyl chloride composite material and a method for preparing the same. The composite material mainly comprises the following components in part by weight: 100 parts of polyvinyl chloride, 3 to 6 parts of stabilizer, 40 to 50 parts of plasticizer, 6 to 10 parts of brominated flame retardant, 6 to 10 parts of zinc borate, 4 to 8 parts of antimony trioxide and 15 to 25 parts of flow modifier. The preparation method comprises the following steps of A: mixing raw materials in a ratio; and B: performing extrusion and granulation. The polyvinyl chloride composite material has quite high fluidity and fire resistance, has excellent heat resistance, weathering resistance and ultraviolet resistance, does not contain phthalic acid and heavy metal and is an environment-friendly polyvinyl chloride composite material.
Description
Technical field
The present invention relates to a kind of polyvinyl chloride composite materials and preparation method thereof, relate in particular to a kind of soft PVC matrix material and preparation method thereof, belong to new material technology field with high workability and high flame resistance.
Background technology
SE (PVC) is the thermoplastic resin that under the initiator effect, is polymerized by vinylchlorid.Because advantages such as SE have the chemical proofing height, electrical insulation capability is good, physical and chemical performance is stable, cheap, it is widely used in each field such as industry, agricultural, traffic, building, communication and health care.But pure SE has certain defective at aspects such as physical strength and flame retardant propertiess, has limited its use.In order to improve the fire-retardant and mechanical property of SE, also need add other component usually, like fire retardant, filler etc.In order to satisfy the requirement of some mechanical property and high flame retardant; The addition of fire retardant and filler is generally all very big; The component of these interpolations usually all can not be well compatible with PVC RESINS; Because the mutual synergistic effect between these additives is not rationally brought into play, need the effect that a large amount of additives just can reach to be needed, thereby cause the processing flowability of final polyvinyl chloride composite materials to reduce greatly on the other hand.
At present aspect the flowability of polyvinyl chloride composite materials and the flame retardant properties certain research is being arranged all, but mostly concentrating on the improvement of an aspect of performance, and ignoring another performance.(publication number is: CN1038660A) relate to filling type polyviny/chloride flow modifier and its producing like one Chinese patent application; The particles of packing material that in pure SE, adds four layers of coating; Improved the processing characteristics of rigid polyvinyl chloride; Yet adopt above-mentioned preparing method's cost higher, the particles of packing material preparation of four layers of coating is complicated, and not good this material simultaneously of flame retardant properties of final material is also unstable to light, heat.One Chinese patent application (publication number: CN101914250A) relate to the preparation method of environmental protection modified polyvinyl chloride master batch with high fluidity and heat stability and for example; Though the modified polyvinyl chloride master batch that this method obtains can carry out the blend granulation with common SE easily, the modified polyvinyl chloride that finally obtains has good processing flowability, thermostability and good mechanical performance.Yet the modified polyvinyl chloride flame retardant properties that adopts aforesaid method to obtain is relatively poor.
And Chinese patent (publication number: CN102061044A) relate to highly anti-impact type fire retarding antistatic polyvinyl chloride compsn and preparation method; The polyvinyl chloride composite materials that this method obtains belongs to mechanically resistant material; Mobile very poor, and the flame retardant properties of the material that obtains by this method is not good enough yet.
And one Chinese patent application (publication number: CN101942156A) relate to high flame retardant polyvinyl chloride cable material and preparation method thereof, make and have high flame-retardant cable and use polyvinyl chloride composite materials through in SE, adding oxyhydroxide, Antimony Trioxide: 99.5Min, the compound zinc borate of P-N type.Yet this method but can not be improved the flowability of polyvinyl chloride composite materials, makes polyvinyl chloride composite materials add difficulty of processing increase in man-hour.
And one Chinese patent application (publication number: CN102286181A) relate to the prescription and preparation method thereof of high workability polyvinyl chloride alloy, this prescription comprises 80～100 parts of SE base-materials, 5～20 parts of toughner, 1～20 part of mineral filler and TPU5～40 part.Through in SE, adding flowability that TPU improves the SE component to obtain to be fit to the SE of injection moulding.Yet this method has only been paid close attention to the flowability of SE, has improved its processing characteristics, and the product that finally prepares according to its prescription and preparation method still has the relatively poor and unsettled shortcoming of flame retardant resistance.
Therefore, can find out that in PVC modified process, improving its flame retardant resistance is the scheme of restraining each other with improving its flowability by above prior art, if the flame retardant resistance improvement, then mobile the reduction, if mobile improvement, then flame retardant resistance reduces.Yet in actual application, the flowability of pvc material and flame retardant resistance are the factor that must consider.Mobile enhancing can improve the processing characteristics of polyvinyl chloride composite materials, is convenient to moulding; Flame retardant properties improves then can expand its Application Areas.For this reason, how under the prerequisite that guarantees high flame resistance, having high workability is the technical bottleneck that needs to be resolved hurrily of polyvinyl chloride composite materials now.
Summary of the invention
The present invention is directed to the existing in prior technology defective, a kind of prescription with high workability, high flame retardant and good comprehensive properties polyvinyl chloride composite materials and preparation method thereof is provided.
The object of the invention can be realized through following technical proposal: a kind of high workability high flame retardant polyvinyl chloride composite materials, this material mainly comprises following component by weight: SE: 100 parts, stablizer: 3～6 parts, softening agent: 40-50 part, bromide fire retardant: 6-10 part, zinc borate: 6-10 part, Antimony Trioxide: 99.5Min: 4-8 part, flow ability modifying agent: 15-25 part.
The PVC RESINS preferred average degree of polymerization of using among the present invention is the resin of 950-1700.
Stablizer can suppress the decomposition reaction of SE under light, thermal environment.The stablizer that the present invention uses can be selected one or more the mixture in calcium-zinc composite stabilizing agent, epoxy soybean oil, calcium stearate, barium stearate or the rare earth composite stabilizer for use.
The plasticising molecular energy of softening agent is inserted between the SE molecular chain; Weaken the stress between the polymer molecular chain; Increase the movability of SE molecular chain, the percent crystallinity of reduction SE molecular chain, thereby plasticity increase, the snappiness of SE are strengthened to improve the SE processing characteristics.。Plasticizer dosage is to influence the mobile significant variable of polyvinyl chloride composite materials; If plasticizer consumption is chosen very few; Then the flowing property of SE can not get guaranteeing, and if plasticizer consumption too much can make the flame retardant properties of polychlorostyrene second matrix material reduce greatly.Operating weight part of the present invention is the softening agent of 40-50 part, under the prerequisite that guarantees the polyvinyl chloride composite materials processing characteristics, does not influence the flame retardant effect of each fire retardant, guarantees that matrix material has high flame retardant properties.
Further; Softening agent of the present invention can be selected phthalic ester plasticizers such as dimixo-octyl phthalate, DINP, n-butyl phthalate for use; Also can select hexanodioic acid ester plasticizers such as PX 208 for use, also can select citric acid ester plasticizers such as Hydrocerol A three positive fourth fat, tributyl acetylcitrate, triethyl citrate for use.Can imagine ground, also can the above-mentioned all kinds of softening agent of enumerating be mixed and use or the different softening agent mixing in every type of softening agent are used.
Among the present invention, bromide fire retardant, zinc borate, Antimony Trioxide: 99.5Min all have fire-retardant effect.Preferably; Bromide fire retardant can select 1 for use, and 2-two (2,4; The 6-tribromophenoxy) ethane or 1; Tribromophenol based flame retardants such as two (pentabromo-phenoxy) ethane of 2-also can select 1 for use, bromo phthalic enhydride based flame retardants such as two (tetrabromo phthalimide) ethane of 2-; Also can select Brominated Polystyrene, ROHM pentabromo-benzyl ester, tetrabromo bisphenol-a epoxy resin oligopolymer, tetrabromo-bisphenol polycarbonate oligopolymer for use, gather bromo superpolymer or bromo oligopolymer based flame retardants such as (2,6-dibromo phenylene ether).Bromide fire retardant of the present invention is not limited to above-mentioned cited; Also can adopt for example hexabromocyclododecane, three (2; The 3-dibromopropyl) bromide fire retardant commonly used on the market such as two (2, the 3-dibromopropyl) fumarates of isocyanuric acid ester, decabrominated dipheny base ethane or dibromo phenyl glycidyl ether.
The zinc borate preferable particle size is that the crystal water content about 3.5 μ m is the zinc borate of 3.5 water, the Antimony Trioxide: 99.5Min of Antimony Trioxide: 99.5Min preferable particle size 1～3 μ m.Purity is high more, and its flame retardant effect is good more.
Can be added in the SE raw material that uses as fire retardant have multiple, yet between the various raw material and promoter action is not all arranged, after some different fire retardant raw materials mix even can produce the effect of cancelling out each other.The present invention chooses bromide fire retardant, zinc borate and Antimony Trioxide: 99.5Min as fire retardant raw material of the present invention through repeatedly testing; The three has the promotion synergistic effect each other; In this flame-retardant system, the fire retardant mechanism that has has: condensed phase fire retardant mechanism, radical-trapping mechanism, coolant mechanism and synergy mechanism.These fire-retardant synergistic effects make fire retardant under the situation of low add-on, also can improve the flame retardant resistance of SE greatly.
Wherein, the boron trioxide, the ZnCl that generate with SE, brominated flame-retardant synergistic after zinc borate at high temperature decomposes
2, ZnBr
2Cover polymer surfaces and form one deck glassy mass, play the effect that suppresses twilight sunset, have the condensed phase fire retardant mechanism.Can improve neat coal amout, be lowered into the cigarette amount, stop burning to be proceeded and decompose the zn cpds that produces.Zinc borate at high temperature absorbs heat to dewater and can also play the effect of cooling fire retardant mechanism.Because zinc borate can be lowered into the cigarette amount, make polyvinyl chloride composite materials of the present invention also have certain hood that presses down in addition.
The bromide fire retardant of high bromine content has good radical-trapping performance.Can know that according to incendiary chain reaction theory keeping burning required is radical, and bromide fire retardant can be caught the radical in the combustion reactions, thereby stop flame transmission that the flame density of combustion zone is descended, combustion reactions is stopped.In addition, bromide fire retardant also has good anti-ultraviolet property.
Antimony Trioxide: 99.5Min has good cooperative flame retardant effect; It makes Organohalogen compounds emit haloid acid or halogen, produces antimony trihalide or halogenation stibo with the weisspiessglanz reaction again, and these antimony compoundss can reduce combustiblematerials and contact with oxygen; The charcoal tectum is generated, thereby reach fire-retardant purpose.
In the composition of raw materials of the present invention; Softening agent need be selected 40-50 part for use; And just 28 parts of the peaks of three based flame retardants, its less consumption explains that the three based flame retardants of the present invention effect of mutually promoting is better, raw material uses less; And need not to use the fire retardant than contaminate environment such as phthalic acid or heavy metal, have environmental protection characteristic preferably.
The present invention is a flowability of improving SE, the flow ability modifying agent that also is added with 15-25 part.Flow ability modifying agent is a vinyl chloride-vinyl acetate copolymer resin.Thereby flow ability modifying agent can not reduce the flowability that the melting index that improves SE under SE finished product rigidity and the flexible prerequisite improves SE.Flow ability modifying agent can be referred to as internal plasticizer with respect to softening agent, and it cooperates with softening agent to strengthen the flowability of SE of the present invention.And vinyl chloride-vinyl acetate copolymer resin since its have tasteless, nontoxic, snappiness is good, Heat stability is good, acid-fast alkali-proof under the normal temperature, the WVTR water vapor trausmission rate advantages of higher is become the preferred flow ability modifying agent of the present invention.Vinyl chloride-vinyl acetate copolymer resin is that vinylchlorid (VC) carries out the polymkeric substance that copolymerization makes with vinyl acetate between to for plastic (VAC) monomer, is commonly called as vinyl chloride-vinyl acetate copolymer resin or vinyl chloride-vinyl acetate resin.Itself and PVC RESINS consistency are good, can improve its kindliness, toughness, hardness and processing flowability.After the flame retardant resistance and flowability that improve polyvinyl chloride composite materials of the present invention, the present invention has also added oxidation inhibitor 0.3-0.5 part, anti UV agent 0.3-0.5 part to improve photostabilization, the weather resistance of polyvinyl chloride composite materials in polyvinyl chloride composite materials.
Oxidation inhibitor can suppress the oxygenolysis of airborne oxygen to polyvinyl chloride composite materials.Suitable oxidation inhibitor can with improve polyvinyl chloride composite materials of the present invention heats the back physicals in the aerobic air reservation after polyvinyl chloride composite materials of the present invention mixes.Among the present invention, oxidation inhibitor can be selected one or both in resistance phenolic antioxidant or the phosphite ester kind antioxidant for use, preferably; Can select four [β-(3 for use; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, the β-positive octadecanol ester of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid or 2; The mixture of one or more in 2 '-thiobis [3-(3, the 5-di-tert-butyl-hydroxy phenyl) ethyl propionate].
Adding anti UV agent is that it has more sensitive chemical reaction to ultraviolet ray because SE is different from other plastics series products.Under outdoor ultraviolet irradiation, SE is easy to produce the decomposition reaction.Thereby the UVA that anti UV agent can will expose on the polrvinyl chloride product suppresses decomposition reaction ultraviolet and SE.Among the present invention; Anti UV agent can be selected from one or both mixture of benzophenone anti UV agent; Preferably, anti UV agent can be selected one or both mixture of UV-531,2-hydroxyl-4-octyloxy UVNUL MS-40,2-hydroxyl-4-methoxy benzophenone or 4-dihydroxy benaophenonel for use.
Further, polyvinyl chloride composite materials of the present invention also comprises lubricant 2-4 part.Lubricant mainly is the processing characteristics that is used for improving SE, reduces frictional force between SE and the processing units, prevents that SE is bonded on the metal-working plant.
Lubricant comprises internal lubricant and external lubricant.It provides the oilness of polyvinyl chloride composite materials in preparation technology; Reduce the internal friction of all components when mixing interpolation so that component mixes; Also reduced the frictional force between polyvinyl chloride composite materials and the metal-working plant simultaneously, prevented that polyvinyl chloride composite materials is bonded on the processing units.Among the present invention, interior lubrication prescription can be selected one or more in saturated hydrocarbons lubricant or the stearic acid lubricant for use; External lubricant can be selected amides lubricant or OPE for use.
Further, in order to prepare the polyvinyl chloride composite materials of different colours, also can add various SE granulations and use toner, for example phthalocyanine blue, dioxazine are consolidated element etc. forever.
The present invention also provides a kind of preparation method who prepares above-mentioned high workability high flame retardant polyvinyl chloride composite materials, and this method may further comprise the steps:
A, batching, batch mixing: take by weighing SE, stablizer, lubricant and softening agent by weight, above-mentioned batching during batch mixing to 110 ℃-120 ℃, is added other component by weight in high speed mixer; Then after high speed mixer high speed batch mixing 1～5 minute, material is added to back discharging about cold mixer cooling and stirring to 45 ℃, be cooled to room temperature;
B, extruding pelletization: join twin screw extruder with above-mentioned through the material behind the batch mixing, melt extrude the back granulation and obtain finished product.
Preferred further; The present invention adopts the conical double screw extruder extruding pelletization, and said conical double-screw main frame one district, main frame two districts, main frame three districts, main frame four districts, main frame five districts, die orifice one district, die orifice two districts, die orifice three district's temperature are respectively 135-145 ℃, 135-140 ℃, 132-135 ℃, 130-135 ℃, 125-130 ℃, 125-130 ℃, 120-125 ℃, 115-120 ℃; Engine speed is 15-20rpm, blanking velocity 10-15rpm.
The salient features of high flame retardant high workability polyvinyl chloride composite materials of the present invention is following: fire-retardant rank reaches the B1 level, testing standard: GB/T5455-1997; Oxygen index is 40～42, testing standard: GB/T5454-1997; The colour fastness grade reaches 5 grades, testing standard: GB/T8427-1998; Shore hardness A is 80～84, testing standard: GB/T7689.4-2001; Melting index is 18～20g/10min, 175 ℃ of probe temperatures, load 9100g, 2.095 millimeters of mouthful moulds.
The present invention compared with prior art has the following advantages:
1, polyvinyl chloride composite materials flowability of the present invention and flame retardant properties are good.Through adding composite flame-retardant agent, make full use of the fire-retardant synergistic effect between the fire retardant, make the flame retardant effect of fire retardant be able to fine performance, under the prerequisite that guarantees the softening agent add-on, realize that the low amount of fire retardant efficiently acts on.
2, add the vinyl chloride-vinyl acetate copolymer resin flow ability modifying agent in the polyvinyl chloride composite materials of the present invention, increase the viscosity of matrix material, improve the processing flowability of matrix material.
3, polyvinyl chloride composite materials of the present invention is heat-resisting, weather-proof, anti-ultraviolet property is good, does not contain phthalic acid, heavy metal free composition, is a kind of novel polyvinyl chloride composite materials of environmental protection.
4, polyvinyl chloride composite materials preparation method technology of the present invention is simple, and handling ease is fit to large-scale industrial production.
Embodiment
Below be specific embodiment of the present invention, technical scheme of the present invention is done further to describe, but the present invention be not limited to these embodiment.
Embodiment 1
Composition of raw materials component and parts by weight thereof are following:
SE: 100 parts
Stablizer: 3 parts
Lubricant: 2 parts
Softening agent: 40 parts
Oxidation inhibitor: 0.3 part
Anti UV agent: 0.3 part
Bromide fire retardant: 6 parts
Antimony Trioxide: 99.5Min: 4 parts
Zinc borate: 6 parts
Vinyl chloride-vinyl acetate copolymer resin: 15 parts
Above-mentioned polyvinyl chloride composite materials raw material prepares through following method:
Batching: distinguish weighing SE, stablizer, lubricant, softening agent by weight.
Batch mixing: above-mentioned batching is stirred to this batch mixing process time-out about 115 degree in high speed mixer.
Reinforced high mixing: add composition remaining in the prescription, after the high speed batch mixing 1～5 minute, get into cold mixer and be cooled to back discharging about 45 degree, be cooled to room temperature.
Extruding pelletization: adopt conical double screw extruder, its main frame one district, main frame two districts, main frame three districts, main frame four districts, main frame five districts, die orifice one district, die orifice two districts, die orifice three district's temperature to be respectively 135-145 ℃, 135-140 ℃, 132-135 ℃, 130-135 ℃, 125-130 ℃, 125-130 ℃, 120-125 ℃, 115-120 ℃; Engine speed is 15-20rpm, blanking velocity 10-15rpm.Extrude directly granulation of back, be cooled to room temperature and promptly get.
The polyvinyl chloride composite materials Main physical performance that makes is seen table one.
Embodiment 2
Composition of raw materials component and parts by weight thereof are following:
SE: 100 parts
Stablizer: 4 parts
Lubricant: 3 parts
Softening agent: 45 parts
Oxidation inhibitor: 0.4 part
Anti UV agent: 0.4 part
Bromide fire retardant: 8 parts
Antimony Trioxide: 99.5Min: 6 parts
Zinc borate: 8 parts
Vinyl chloride-vinyl acetate copolymer resin: 18 parts
The preparation method of above-mentioned polyvinyl chloride composite materials raw material is identical with embodiment one, and the Main physical performance of the polyvinyl chloride composite materials for preparing is seen table one.
Embodiment 3
Composition of raw materials component and parts by weight thereof are following:
SE: 100 parts
Stablizer: 5 parts
Lubricant: 5 parts
Softening agent: 48 parts
Oxidation inhibitor: 0.5 part
Anti UV agent: 0.4 part
Bromide fire retardant: 10 parts
Antimony Trioxide: 99.5Min: 6 parts
Zinc borate: 10 parts
Vinyl chloride-vinyl acetate copolymer resin: 22 parts
The preparation method of above-mentioned polyvinyl chloride composite materials raw material is identical with embodiment one, and the Main physical performance of the polyvinyl chloride composite materials for preparing is seen table one.
Embodiment 4
Composition of raw materials component and parts by weight thereof are following:
SE: 100 parts
Stablizer: 6 parts
Lubricant: 4 parts
Softening agent: 50 parts
Oxidation inhibitor: 0.5 part
Anti UV agent: 0.5 part
Bromide fire retardant: 10 parts
Antimony Trioxide: 99.5Min: 8 parts
Zinc borate: 10 parts
Vinyl chloride-vinyl acetate copolymer resin: 25 parts
The preparation method of above-mentioned polyvinyl chloride composite materials raw material is identical with embodiment one, and the Main physical performance of the polyvinyl chloride composite materials for preparing is seen table one.
Comparative example 1
Composition of raw materials component and parts by weight thereof are following:
SE: 100 parts
Stablizer: 3.5 parts
Lubricant: 3 parts
Softening agent: 45 parts
Oxidation inhibitor: 0.4 part
Anti UV agent: 0.4 part
Bromide fire retardant: 0 part
Antimony Trioxide: 99.5Min: 6 parts
Zinc borate: 0 part
Vinyl chloride-vinyl acetate copolymer resin: 18 parts
Its preparation method is identical with embodiment one, and the Main physical performance of the goods that make is seen table one.
Comparative example 2
Composition of raw materials component and parts by weight thereof are following:
SE: 100 parts
Stablizer: 3.5 parts
Lubricant: 3 parts
Softening agent: 45 parts
Oxidation inhibitor: 0.4 part
Anti UV agent: 0.4 part
Bromide fire retardant: 8 parts
Antimony Trioxide: 99.5Min: 6 parts
Zinc borate: 8 parts
Vinyl chloride-vinyl acetate copolymer resin: 0 part
Its preparation method is identical with embodiment one, and the Main physical performance of the goods that make is seen table one.
Comparative example 3
Composition of raw materials component and parts by weight thereof are following:
SE: 100 parts
Stablizer: 3.5 parts
Lubricant: 3 parts
Softening agent: 45 parts
Oxidation inhibitor: 0.4 part
Anti UV agent: 0.4 part
Bromide fire retardant: 0 part
Antimony Trioxide: 99.5Min: 6 parts
Zinc borate: 0 part
Vinyl chloride-vinyl acetate copolymer resin: 0 part
Its preparation method is identical with embodiment one, and the Main physical performance of the goods that make is seen table one.
Comparative example 4
Composition of raw materials component and parts by weight thereof are following:
SE: 100 parts
Stablizer: 3.5 parts
Lubricant: 3 parts
Softening agent: 45 parts
Oxidation inhibitor: 0.4 part
Anti UV agent: 0.4 part
Bromide fire retardant: 8 parts
Antimony Trioxide: 99.5Min: 6 parts
Zinc borate: 0 part
Vinyl chloride-vinyl acetate copolymer resin: 0 part
Its preparation method is identical with embodiment one, and the Main physical performance of the goods that make is seen table one.
Table one; The physicals of vinylchlorid matrix material
Annotate: the melting index test condition: 175 ℃ of probe temperatures, load 9100g, 2.095 millimeters of mouthful moulds.
Visible from table one, prepared its weather resistance of polyvinyl chloride composite materials of the present invention is good, has higher flame retardant properties and processing flowability.The synergistic effect that can find out three kinds of fire retardants from comparative example does not clearly add bromide fire retardant or zinc borate, and its flame retardant effect reduces greatly, sees comparative example 1,3,4.Vinyl chloride-vinyl acetate copolymer resin is mobile most important to this composite system, does not add this properties-correcting agent, and the flowing property of matrix material reduces greatly, sees comparative example 2,3,4
Specific embodiment described herein only is that the present invention's spirit is illustrated.Person of ordinary skill in the field of the present invention can make various modifications or replenishes 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.
Claims (10)
1. high workability high flame retardant polyvinyl chloride composite materials, this material comprises following component by weight: SE: 100 parts, stablizer: 3～6 parts, softening agent: 40-50 part, bromide fire retardant: 6-10 part, zinc borate: 6-10 part, Antimony Trioxide: 99.5Min: 4-8 part, flow ability modifying agent: 15-25 part.
2. high workability high flame retardant polyvinyl chloride composite materials according to claim 1 is characterized in that: the mean polymerisation degree of said SE is 950-1700.
3. the prescription of high workability high flame retardant polyvinyl chloride matrix material according to claim 1 is characterized in that: said stablizer is one or more in calcium-zinc composite stabilizing agent, epoxy soybean oil, calcium stearate, barium stearate, the rare earth composite stabilizer.
4. high workability high flame retardant polyvinyl chloride composite materials according to claim 1 is characterized in that: said softening agent is one or more mixtures in phthalic ester plasticizer, hexanodioic acid ester plasticizer or the citric acid ester plasticizer.
5. high workability high flame retardant polyvinyl chloride composite materials according to claim 1; It is characterized in that: said bromide fire retardant is tribromophenol based flame retardant, bromophthalic acid acid anhydride based flame retardant, bromo high polymer flame retardant, bromo oligopolymer based flame retardant, hexabromocyclododecane flame retardant, three (2; The 3-dibromopropyl) one or more mixing in isocyanuric acid ester fire retardant, decabrominated dipheny base ethane fire retardant, two (2, the 3-dibromopropyl) the fumarate fire retardants of dibromo phenyl glycidyl ether.
6. high workability high flame retardant polyvinyl chloride composite materials according to claim 1 is characterized in that: described zinc borate is that the crystal water content about particle diameter 3.5 μ m is the zinc borate of 3.5 water; The Antimony Trioxide: 99.5Min of described Antimony Trioxide: 99.5Min preferable particle size 1～3 μ m.
7. high workability high flame retardant polyvinyl chloride composite materials according to claim 1 is characterized in that: said flow ability modifying agent is a vinyl chloride-vinyl acetate copolymer resin.
8. according to each described high workability high flame retardant polyvinyl chloride composite materials of claim 1 to 7, it is characterized in that: this matrix material also comprises oxidation inhibitor by weight: 0.3-0.5 part, anti UV agent: 0.3-0.5 part, lubricant 2-4 part.
9. the preparation method of a high workability high flame retardant polyvinyl chloride composite materials as claimed in claim 8, this method may further comprise the steps:
A, batching, batch mixing: take by weighing SE, stablizer, lubricant and softening agent by weight,, during high speed batch mixing to 110 ℃-120 ℃, add other component by weight with above-mentioned batching batch mixing for the first time in high speed mixer; In high speed mixer, after the batch mixing 1～5 minute, material is added to cold mixer is cooled to back discharging about 45 ℃ then, be cooled to room temperature;
B, extruding pelletization: join twin screw extruder through the material behind the batch mixing and melt extrude the back granulation and obtain finished product with above-mentioned.
10. the preparation method of high workability high flame retardant polyvinyl chloride composite materials according to claim 9; It is characterized in that: step B twin screw extruder, its main frame one district, main frame two districts, main frame three districts, main frame four districts, main frame five districts, die orifice one district, die orifice two districts, die orifice three district's temperature are respectively 140 ℃, 138 ℃, 135 ℃, 132 ℃, 130 ℃, 130 ℃, 125 ℃, 120 ℃; Engine speed is 17rpm, blanking velocity 11rpm.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924850A (en) * | 2012-11-20 | 2013-02-13 | 苏州奥凯材料技术有限公司 | Polyvinyl chloride transparent weather-resistant sheet |
| CN103788535A (en) * | 2014-01-07 | 2014-05-14 | 苏州奥凯材料技术有限公司 | Hydrous iron hydroxide synergic inflaming-retarding smoke-inhibiting PVC/PVCA (Polyvinyl Chloride/Poly Vinyl Chloride Acetate) sheet material |
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| CN104004297A (en) * | 2014-06-06 | 2014-08-27 | 潘衍军 | High-flame retardance soft glue clothing label material and method for manufacturing labels by using same |
| CN104031326A (en) * | 2013-03-07 | 2014-09-10 | 苑初明 | Modified hard crosslinked polyvinyl chloride flame-retardant foam and preparation method thereof |
| CN104109304A (en) * | 2014-06-23 | 2014-10-22 | 安徽荣玖光纤通信科技有限公司 | High-fluidity PVC cable material and preparation method thereof |
| CN104177724A (en) * | 2013-05-21 | 2014-12-03 | 保定维赛复合材料科技有限公司 | Modified conductive hard crosslinked polyvinyl chloride foam and preparation method thereof |
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| CN105647071A (en) * | 2016-04-08 | 2016-06-08 | 苏州新区华士达工程塑胶有限公司 | Packaging plastic thin film with flame retardant effect |
| CN108250623A (en) * | 2018-01-24 | 2018-07-06 | 杭州余杭南湖塑料制品厂 | A kind of Low temperature-resistanflexible flexible PVC plastic and preparation method |
| CN109021436A (en) * | 2018-06-29 | 2018-12-18 | 江苏德溢利新材料科技有限公司 | A kind of Novel flame retardant plastic photovoltaic bracket |
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| WO2020233027A1 (en) * | 2019-05-17 | 2020-11-26 | 宁波先锋新材料股份有限公司 | Coating composite material and manufacturing method therefor |
| WO2020233028A1 (en) * | 2019-05-22 | 2020-11-26 | 宁波先锋新材料股份有限公司 | Flame-retardant and smoke-suppressing soft polyvinyl chloride composite material having good mechanical performance and preparation method therefor |
| CN112795085A (en) * | 2020-12-28 | 2021-05-14 | 上海日之升科技有限公司 | Precipitation-resistant flame-retardant polypropylene composite material in high-temperature and high-humidity environment and preparation method thereof |
| CN114058138A (en) * | 2021-12-07 | 2022-02-18 | 南京曼润高分子科技研究院有限公司 | Super wear-resistant PVC material for conveying belt |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102924850A (en) * | 2012-11-20 | 2013-02-13 | 苏州奥凯材料技术有限公司 | Polyvinyl chloride transparent weather-resistant sheet |
| CN104031326A (en) * | 2013-03-07 | 2014-09-10 | 苑初明 | Modified hard crosslinked polyvinyl chloride flame-retardant foam and preparation method thereof |
| CN104031326B (en) * | 2013-03-07 | 2016-08-10 | 苑初明 | A kind of modified hard cross-linked polrvinyl chloride flame-retardant foam and preparation method thereof |
| CN104177724B (en) * | 2013-05-21 | 2016-08-10 | 保定维赛复合材料科技有限公司 | A kind of denatured conductive type hard crosslinked polyvinyl chloride foam and preparation method thereof |
| CN104177724A (en) * | 2013-05-21 | 2014-12-03 | 保定维赛复合材料科技有限公司 | Modified conductive hard crosslinked polyvinyl chloride foam and preparation method thereof |
| CN103788535A (en) * | 2014-01-07 | 2014-05-14 | 苏州奥凯材料技术有限公司 | Hydrous iron hydroxide synergic inflaming-retarding smoke-inhibiting PVC/PVCA (Polyvinyl Chloride/Poly Vinyl Chloride Acetate) sheet material |
| CN103788535B (en) * | 2014-01-07 | 2016-03-23 | 苏州奥凯高分子材料股份有限公司 | Hydration hydrous iron oxide synergy fire-resistant smoke-inhibiting PVC/PVCA sheet material |
| CN103897296A (en) * | 2014-03-24 | 2014-07-02 | 安徽冠泓塑业有限公司 | Low-cost flame-retardant PVC (Polyvinyl Chloride) modified plastic composition |
| CN104004297A (en) * | 2014-06-06 | 2014-08-27 | 潘衍军 | High-flame retardance soft glue clothing label material and method for manufacturing labels by using same |
| CN104109304A (en) * | 2014-06-23 | 2014-10-22 | 安徽荣玖光纤通信科技有限公司 | High-fluidity PVC cable material and preparation method thereof |
| CN104109304B (en) * | 2014-06-23 | 2016-08-24 | 安徽荣玖光纤通信科技有限公司 | A kind of high flowing polyvinyl chloride cable material and preparation method thereof |
| CN104945766A (en) * | 2015-05-19 | 2015-09-30 | 苏州德翔装饰工程有限公司 | Composite high polymer material for kitchen top plates and preparation method thereof |
| CN105647071A (en) * | 2016-04-08 | 2016-06-08 | 苏州新区华士达工程塑胶有限公司 | Packaging plastic thin film with flame retardant effect |
| CN108250623A (en) * | 2018-01-24 | 2018-07-06 | 杭州余杭南湖塑料制品厂 | A kind of Low temperature-resistanflexible flexible PVC plastic and preparation method |
| CN109021436A (en) * | 2018-06-29 | 2018-12-18 | 江苏德溢利新材料科技有限公司 | A kind of Novel flame retardant plastic photovoltaic bracket |
| CN109517290A (en) * | 2018-09-12 | 2019-03-26 | 谢彪 | A kind of high transparency trachea cannula special-purpose polychloroethylene pellet |
| WO2020233027A1 (en) * | 2019-05-17 | 2020-11-26 | 宁波先锋新材料股份有限公司 | Coating composite material and manufacturing method therefor |
| WO2020233028A1 (en) * | 2019-05-22 | 2020-11-26 | 宁波先锋新材料股份有限公司 | Flame-retardant and smoke-suppressing soft polyvinyl chloride composite material having good mechanical performance and preparation method therefor |
| CN112795085A (en) * | 2020-12-28 | 2021-05-14 | 上海日之升科技有限公司 | Precipitation-resistant flame-retardant polypropylene composite material in high-temperature and high-humidity environment and preparation method thereof |
| CN114058138A (en) * | 2021-12-07 | 2022-02-18 | 南京曼润高分子科技研究院有限公司 | Super wear-resistant PVC material for conveying belt |
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