CN1296033A - Process for preparation of polyvinyl-chloride foaming material - Google Patents
Process for preparation of polyvinyl-chloride foaming material Download PDFInfo
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- CN1296033A CN1296033A CN 99123815 CN99123815A CN1296033A CN 1296033 A CN1296033 A CN 1296033A CN 99123815 CN99123815 CN 99123815 CN 99123815 A CN99123815 A CN 99123815A CN 1296033 A CN1296033 A CN 1296033A
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Abstract
A production method of PVC foamed plastics includes the following steps: proportioning PVC resin or PVC-graft resin, plasticizer, foaming agent and adjuvant according to its formula, uniformly stirring and mixing, double roller open mixing or enclosed mixing, extruding by using twin screw extruder machine, a plasticization, melting, foaming, cooling and cutting so as to obtain the invented product with high foaming multiplying power.
Description
The present invention relates to a kind of preparation method of high foamability foam material.More particularly, the present invention relates to the preparation method of polyvinyl chloride (PVC) high foamability foam material.
As everyone knows, porous plastics be a kind of be the matrix material of filler with gas, compare with plastics, it has many valuable performances, as light weight, specific tenacity height, to absorb the strong and heat-insulating sound-insulating of shock load ability effective etc.Therefore, in industries such as automobile, electronics, chemical industry and machinery, be extensive use of.
Because the method that the molecular structure of various resins adopts during with microscopic pattern and foaming is different, thus cause melt tension different with elasticity, thereby directly influence the multiplying power when plastic foamed.Some material for example polyethylene (PE), urethane (PU) more easily foams, and expansion ratio can reach about 20 times.When the chemical process of some material as PVC adopts foamed, expansion ratio can only reach 3-4 doubly, and it is just very difficult to increase multiplying power again.
In order to improve the expansion ratio of plastic material, two kinds of methods are arranged roughly: a kind of method is the resin of exploitation high fondant-strength, as the PP-FAS-814 of U.S. Himont company; Another kind method is to improve existing foaming method.
Company of Total France adopts freonll-11 and chemical foaming to combine, and obtains the PVC foam material of 20-27 times of expansion ratio with two steps or three-step approach foaming.
There are the dielectric expansion of employing method in Korea S and the Mitsubishi company of changing into, the PVC material of preparation high foamability.Also having the part Study personnel to adopt blending resin to make expansion ratio is PVC material about 6 times.
We are through research chronically, and chemical foaming agent is adopted in test repeatedly, and making unit weight by two step foamings and a step foaming (another part application) is 50-240kg/m
3, expansion ratio is the PVC foam material of the high foamability more than 20 times.
Therefore, order of the present invention provides the manufacture method of the PVC foam material of high foamability.
More particularly, method provided by the invention is the blending resin extrusion molding.Described blending resin extrusion molding is that polyvinyl chloride resin or PVC-graft resin, softening agent, whipping agent, foam stabilizer, processing aid, filler and pigment are mixed, after making powdery mixing raw material material, through opening refining or banburying, shred or particle, again in screw extrusion press, after head is extruded into sheet material, send into drying tunnel, in drying tunnel, under 110-240 ℃ of temperature, behind plasticizing and melt foaming, cooling obtains the different PVC foam material product of expansion ratio with cutting.
Prescription raw materials used in the inventive method is:
Formulation weight part
Polyvinyl chloride resin or
PVC-graft resin 100
Softening agent 35-120
Linking agent 0.1-5
Whipping agent 5-20
Foam stabilizer 0-10
Thermo-stabilizer 0.5-10
Filler 0.5-50
Pigment is an amount of.
Used raw material polyvinyl chloride resin is selected from least a or its several resins in suspension polymerization polyvinyl chloride resin, suspension continuous polymerization polyvinyl chloride resin, the composition group in the inventive method.
Employed in the methods of the invention softening agent is crucial.Employed softening agent is selected from by n-butyl phthalate (DBP) in the inventive method, dinoctyl phthalate (DOP), didecyl phthalate (DDP), Phthalic acid, diallyl ester (DAP), diethyl phthalate (DEP), diheptyl phthalate (DHP), diphenyl phthalate (DPP), dimethyl phthalate, diisobutyl phthalate (DMP), dimixo-octyl phthalate (DIOP), at least a or its combination in diisooctyl isophthalate (DIOIP) or the dioctyl isophthalate composition group.Its consumption is 100 weight parts by polyvinyl chloride resin, and softening agent is the 35-120 weight part, is preferably the 40-100 weight part, more preferably the 50-90 weight part.When plasticizer consumption was less than 35 weight parts, expansion ratio was low, and when plasticizer dosage surpassed 120 weight parts, expansion ratio began to reduce, and this may be because the viscosity of system is excessive or too smallly all be unfavorable for high foaming.Certainly, the temperature of system is also very important to high foamability.
Have been found that, linking agent and polyfunctional monomer are the important component of co-mixing system, employed in the method for the invention linking agent is selected from dicumyl peroxide (DCP) or benzoyl peroxide, its consumption is for pressing polyvinyl chloride resin 100 weight parts, linking agent is the 0.1-5 weight part, be preferably the 0.5-4 weight part, more preferably the 1-3 weight part.
The consumption of whipping agent is one of important factor of decision foam unit weight and abscess quality.In the methods of the invention, employed whipping agent is that gas forming amount is big, the high organic blowing agent of foaming efficient.For co-mixing system, product requirement reaches high foamability, selects efficient aerating powder also very important.Whipping agent of the prior art can be divided into: (1) azo compound; (2) N-nitroso compound; (3) hydrazide kind compound; (4) urea derivative; (5) triazo-compound etc.Employed whipping agent is selected from the inferior methyne tetramine of Cellmic C 121 (AC), dinitroso, at least a or several in sulfonyloxy methyl amine, 22 '-Diisopropyl azodicarboxylate (AZDN), 44 '-bis oxide benzol sulfohydrazide or the sodium bicarbonate composition group in the inventive method.Its consumption is pressed polyvinyl chloride resin 100 weight parts, and whipping agent is the 5-20 weight part, is preferably the 7-18 weight part, more preferably the 9-14 weight part.Be lower than 5 weight parts, the expansion ratio that misses one's aim is higher than 20 weight parts, and expansion ratio and abscess quality can descend on the contrary.This is because whipping agent can exothermic cause in decomposition course.Whipping agent is many more, and it is big more to foam, and the heat of generation is just many more.When abscess formation in a single day, abscess has just become hot poor conductor, and it makes melt viscosity and melt tension descend, and at this moment also steeping to break to steep greatly increases, so expansion ratio descends on the contrary.
Foam stabilizer can make uniform in foaming, uses in the methods of the invention and also can not use foam stabilizer.If use, its consumption is pressed polyvinyl chloride resin 100 weight parts, and foam stabilizer is the 0-10 weight part, is preferably the 1-9 weight part, more preferably the 3-8 weight part.Foam stabilizer is selected from by methyl-silicone oil, phenyl silicone oil, tolyl silicone oil or containing hydrogen silicone oil forms at least a or several in the group.
Owing to the defective of polyvinyl chloride molecular chain itself, cause the poor heat stability of polyvinyl chloride molecule.For foaming process is successfully carried out, added thermo-stabilizer in the inventive method, its consumption is pressed polyvinyl chloride resin 100 weight parts, and thermo-stabilizer is the 0.5-10 weight part, is preferably the 1-8 weight part, more preferably the 3-7 weight part.Employed stablizer is selected from by the base lead salt class in the inventive method, as dibasic lead stearate, second base lead sulfate or dibasic lead phosphite; The metallic soap class is as calcium stearate, barium stearate, cadmium stearate, Zinic stearas, lead stearate or cadmium laurate; Organic tin is as dibutyl tin laurate, toxilic acid dioctyltin, two lauric acid, two positive phenyltins, two (the different monooctyl ester of sulfo-glycolic acid) two positive phenyltins or two (the different monooctyl ester of sulfo-glycolic acid) di-n-butyl tin; One package stabilizer is as at least a or its combination in liquid organic calcium zinc complexes, the organic barium zinc complexes of liquid or the organic barium cadmium of the liquid mixture composition group.
Employed in the present invention processing aid also has lubricant, filler and pigment etc. except thermo-stabilizer.They all are well-known in the art.For example, use proper amount of lubricating agent, it is selected from stearic acid and ester class such as stearic acid; The metallic soap class is as calcium stearate, barium stearate, cadmium stearate, Zinic stearas or lead stearate; Hydro carbons is as a kind of or its combination in paraffin, polyethylene wax or the oxidic polyethylene composition group.Used filler in the inventive method, press polyvinyl chloride resin 100 weight parts, amount of filler is the 0.5-50 weight part, is preferably the 1-40 weight part, 10-35 weight part more preferably, filler can be selected from least a or several in talcum powder, silicon-dioxide, lime carbonate or the wollastonite composition group.
Method of the present invention can be with very high efficient, with the device fabrication PVC porous plastics of suitable treatment plastics.Method of the present invention is to comprise general raw materials such as processing aid in polyvinyl chloride resin or PVC-graft resin, softening agent, whipping agent and the technological process, after the prescription metering, adds in the steel basin.Under 70 ℃-100 ℃ temperature,, make it generate powdered mixing raw material material with 500-1000 rev/min of stirring raw mix.
The powdery mixing raw material material for preparing is carried out fusion open refining or banburying, make each the component thorough mixing in the raw material, shred then or particle.
Material through opening refining or banburying adds in the screw extrusion press, after head is extruded into sheet material, sends into drying tunnel, in drying tunnel, under 110-240 ℃ of temperature, after plasticizing and foaming, makes product P VC porous plastics, and its performance is as follows:
Thickness 2-8mm
Appearance white, micropore, foam are even
Density~100kg/m
3
Can ratio-frequency welding, fire-retardant
Mechanical property:
Tensile strength 〉=0.2Mpa
Elongation at break 〉=100%
Compressive strength P50/l 〉=20KPa
The device of implementing the inventive method is a device general in the present technique field, as two roller mills (Shanghai plastics machinery factory) and homogenizer GH-10 type (Beijing plastics machinery factory) etc.
Testing sequence is:
(1) step of preparation mixing raw material material
In steel basin, polyvinyl chloride resin, blending resin, auxiliary agent and filler etc. by after the prescription metering, are added homogenizer, to be lower than 70 ℃-100 ℃, be preferably continuously stirring under 80 ℃-90 ℃ the temperature, add softening agent, thorough mixing prepares mixed uniformly mixing raw material material;
(2) two rollers are opened refining or banburying step
Mixing raw material material with step (1) preparation at 90 ℃-130 ℃, is preferably under 100 ℃ of-120 ℃ of temperature and carries out melting or banburying, make each component thorough mixing after, shred or particle;
(3) extrusion foaming step
To add temperature be 80 ℃-130 ℃ with opening material after refining or the banburying, is preferably in 90 ℃-120 ℃ the screw extrusion press, extrudes in flakes through head.This sheet material is sent into temperature remain on 180 ℃-240 ℃ and be preferably in 200 ℃-240 ℃ the drying tunnel foamable continuously, make the uniform foam sheet of thickness.
Further describe the present invention with embodiment below.These examples are preferred embodiment of the invention, are not construed as limiting the invention.
Test conditions as mentioned above.Those skilled in the art can select arbitrarily in above-mentioned scope.Therefore, in the listed examples table, no longer repeat.
Embodiment | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 |
PVC-grafting (weight part) | ???100 | ???100 | ????- | ????- | ????- | ????- | ????- |
PVC (weight part) | ????- | ????- | ????100 | ????100 | ????100 | ????100 | ????100 |
EVA (weight part) | ????- | ????- | ????- | ????- | ????60 | ????60 | ????50 |
LDPE (weight part) | ????- | ????- | ????- | ????- | ????100 | ????25 | ????50 |
D0P (weight part) | ????70 | ????50 | ????- | ????40 | ????- | ????30 | ????50 |
DBP (weight part) | ????- | ????- | ????50 | ????- | ????50 | ????10 | ????- |
DAP (weight part) | ????- | ????20 | ????20 | ????40 | ????- | ????10 | ????20 |
BP0 (weight part) | ????- | ????- | ????2 | ????- | ????2 | ????- | ????- |
DCP (weight part) | ????2 | ????2 | ????- | ????2 | ????- | ????2 | ????2 |
AC (weight part) | ????20 | ????20 | ????20 | ????20 | ????20 | ????20 | ????20 |
Lead salt (weight part) | ????5 | ????- | ????- | ????5 | ????5 | ????- | ????- |
Organotin (weight part) | ????- | ????5 | ????6 | ????- | ????- | ????5 | ????5 |
Lime carbonate (weight part) | ????5 | ????3 | ????- | ????5 | ????- | ????5 | ????3 |
Talcum powder (weight part) | ????- | ????2 | ????5 | ????- | ????3 | ????- | ????- |
Silicon oxide (weight part) | ????- | ????- | ????- | ????- | ????2 | ????- | ????2 |
The result | ????- | ????- | ????- | ????- | ????- | ????- | ????- |
Spumescence | ????○ | ????○ | ????□ | ????□ | ????○ | ????□ | ????□ |
Unit weight (Kg/m 3) | ????48 | ????54 | ????82 | ????89 | ????67 | ????79 | ????86 |
After the description of reading above, those skilled in the art can make improvements or revise the present invention the present invention, only otherwise leave spirit of the present invention, and all within the scope of the invention.Scope of the present invention is proposed by the appended claims.
Claims (15)
1. the production method of a high foamability PVC porous plastics, this method comprises:
By following prescription
Formulation weight part
Polyvinyl chloride resin or
PVC-graft resin 100
Softening agent 35-120
Whipping agent 5-20
Linking agent 0.1-5
Foam stabilizer 0-10
Filler 0.5-50
Thermo-stabilizer 0.5-10
An amount of and the following steps of pigment: the step of (1) preparation mixing raw material material
In steel basin, polyvinyl chloride resin, blending resin, auxiliary agent and filler etc. by after the prescription metering, are added homogenizer, continuously stirring under 70 ℃-100 ℃ temperature adds softening agent, and thorough mixing prepares mixed uniformly mixing raw material material;
(2) two rollers are opened refining or banburying step
Mixing raw material material with step (1) preparation carries out melting or banburying under 90 ℃-130 ℃ temperature, make each component thorough mixing after, shred or particle;
(3) extrusion foaming step
To add temperature be in 80 ℃-130 ℃ the screw extrusion press with opening material after refining or the banburying, extrudes in flakes through head, and this sheet material is sent into continuous foamable in the drying tunnel that temperature remains on 180 ℃-240 ℃, makes the uniform foam sheet of thickness.
2. by the production method of the described PVC porous plastics of claim 1, wherein said prescription is:
Formulation weight part
Polyvinyl chloride resin or
PVC-graft resin 100
Softening agent 40-100
Whipping agent 7-18
Linking agent 0.5-4
Foam stabilizer 1-9
Filler 1-40
Thermo-stabilizer 1-8
Pigment is an amount of.
3. by the production method of the described PVC porous plastics of claim 1, wherein said prescription is:
Formulation weight part
Polyvinyl chloride resin or
PVC-graft resin 100
Softening agent 50-90
Whipping agent 9-14
Linking agent 1-3
Foam stabilizer 3-8
Filler 10-35
Thermo-stabilizer 3-7
Pigment is an amount of.
4. by at least a or its several resins in the described PVC suspension emulsion of claim 1 continuous polymerization polyvinyl chloride resin, the composition group.
5. by the production method of the described PVC porous plastics of claim 1, wherein softening agent is selected from by n-butyl phthalate, dinoctyl phthalate, didecyl phthalate, Phthalic acid, diallyl ester, diethyl phthalate, diheptyl phthalate, diphenyl phthalate, dimethyl phthalate, diisobutyl phthalate, dimixo-octyl phthalate, diisooctyl isophthalate or dioctyl isophthalate and forms at least a or its combination in the group.
6. by the preparation method of the described PVC porous plastics of claim 1, wherein whipping agent is selected from Cellmic C 121, the inferior methyne tetramine of dinitroso, at least a or several in sulfonyloxy methyl amine or the Diisopropyl azodicarboxylate composition group.
7. by the production method of the described PVC porous plastics of claim 1, wherein filler is selected from by talcum, silicon oxide, lime carbonate or wollastonite and forms at least a or its combination in the group.
8. by the production method of the described PVC porous plastics of claim 1, wherein said whipping agent is selected from by Cellmic C 121, the inferior methyne tetramine of dinitroso, sulfonyloxy methyl amine, 22 '-Diisopropyl azodicarboxylate, 44 '-bis oxide benzol sulfohydrazide or sodium bicarbonate is formed at least a or several in the group.
9. by the production method of the described PVC porous plastics of claim 1, wherein said foam stabilizer is selected from by methyl-silicone oil, phenyl silicone oil, tolyl silicone oil or containing hydrogen silicone oil forms at least a or several in the group.
10. by the production method of the described PVC porous plastics of claim 1, wherein said thermo-stabilizer is selected from by the base lead salt class, as dibasic lead stearate, second base lead sulfate or dibasic lead phosphite; The metallic soap class is as calcium stearate, barium stearate, cadmium stearate, Zinic stearas, lead stearate or cadmium laurate; Organic tin is as dibutyl tin laurate, toxilic acid dioctyltin, two lauric acid, two positive phenyltins, two (the different monooctyl ester of sulfo-glycolic acid) two positive phenyltins or two (the different monooctyl ester of sulfo-glycolic acid) di-n-butyl tin; One package stabilizer is as at least a or its combination in liquid organic calcium zinc complexes, the organic barium zinc complexes of liquid or the organic barium cadmium of the liquid mixture composition group.
11. by the production method of the described PVC porous plastics of claim 1, at least a or several in the optional free skating stone flour of wherein said filler, silicon-dioxide, lime carbonate or the wollastonite composition group.
12. by the production method of the described PVC porous plastics of claim 1, when wherein mixing, the temperature of described raw mix material remains on 80 ℃-90 ℃.
13. by the production method of the described PVC porous plastics of claim 1, the temperature in the wherein said drying tunnel is 200 ℃-240 ℃.
14. by the production method of the described PVC porous plastics of claim 1, wherein said pair of roller mixing temperature is 100 ℃-120 ℃.
15. by the production method of the described PVC porous plastics of claim 1, the temperature of wherein said forcing machine is 90 ℃-120 ℃.
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CN 99123815 CN1118506C (en) | 1999-11-12 | 1999-11-12 | Process for preparation of polyvinyl-chloride foaming material |
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CN 99123815 CN1118506C (en) | 1999-11-12 | 1999-11-12 | Process for preparation of polyvinyl-chloride foaming material |
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CN1118506C CN1118506C (en) | 2003-08-20 |
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CN102585394A (en) * | 2011-12-05 | 2012-07-18 | 山东慧科助剂股份有限公司 | Calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof |
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JP2014098135A (en) * | 2012-10-16 | 2014-05-29 | Hitachi Metals Ltd | Soft vinyl chloride resin composition, and electric wire and cable using the same |
CN104004302A (en) * | 2014-06-13 | 2014-08-27 | 山东日科化学股份有限公司 | Low-density polyvinyl chloride foaming material and preparation method thereof |
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CN108659402A (en) * | 2018-06-04 | 2018-10-16 | 辅创科技(宜昌)有限公司 | A kind of soft foam polyvinyl chloride plastics of low-density and preparation method |
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CN112194867A (en) * | 2020-10-27 | 2021-01-08 | 惠州市众益电子辅料有限公司 | High-foaming sound insulation material for vehicle and preparation method thereof |
CN114656727A (en) * | 2020-12-22 | 2022-06-24 | 韩华思路信(株) | Foamable vinyl chloride resin composition |
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1999
- 1999-11-12 CN CN 99123815 patent/CN1118506C/en not_active Expired - Lifetime
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CN102585394A (en) * | 2011-12-05 | 2012-07-18 | 山东慧科助剂股份有限公司 | Calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof |
CN102585394B (en) * | 2011-12-05 | 2014-02-26 | 山东慧科助剂股份有限公司 | Calcium-zinc molecular sieve composite stabilizer for vinyl chloride and preparation method thereof |
JP2014098135A (en) * | 2012-10-16 | 2014-05-29 | Hitachi Metals Ltd | Soft vinyl chloride resin composition, and electric wire and cable using the same |
CN103172952A (en) * | 2013-04-08 | 2013-06-26 | 陕西理工学院 | Preparation method of coal ash-resin composite material suitable for extrusion molding |
CN103172952B (en) * | 2013-04-08 | 2015-07-29 | 陕西理工学院 | A kind of preparation method being applicable to the flyash-resin composite materials of extrusion moulding |
CN103420031A (en) * | 2013-07-24 | 2013-12-04 | 桐城运城制版有限公司 | Packaging material |
CN104004302A (en) * | 2014-06-13 | 2014-08-27 | 山东日科化学股份有限公司 | Low-density polyvinyl chloride foaming material and preparation method thereof |
CN104988743A (en) * | 2015-06-12 | 2015-10-21 | 安徽安利材料科技股份有限公司 | White PVC slice for testing pigment migration of synthetic leather substrate and preparation method thereof |
CN105924838A (en) * | 2016-05-30 | 2016-09-07 | 熊涛 | PVC white foam decorative material and processing method thereof |
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CN108659402A (en) * | 2018-06-04 | 2018-10-16 | 辅创科技(宜昌)有限公司 | A kind of soft foam polyvinyl chloride plastics of low-density and preparation method |
CN109184068A (en) * | 2018-08-29 | 2019-01-11 | 重庆品联工艺品有限公司 | A kind of novel integrated wall plate of assembled and its production method |
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