CN103788461A - Method for preparing synthetic paper based on ultrahigh-molecular weight polyethylene - Google Patents
Method for preparing synthetic paper based on ultrahigh-molecular weight polyethylene Download PDFInfo
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- CN103788461A CN103788461A CN201410058230.3A CN201410058230A CN103788461A CN 103788461 A CN103788461 A CN 103788461A CN 201410058230 A CN201410058230 A CN 201410058230A CN 103788461 A CN103788461 A CN 103788461A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/04—Ingredients treated with organic substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
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Abstract
The invention relates to a method for preparing synthetic paper based on ultrahigh-molecular weight polyethylene. The method comprises the following steps: modifying an inorganic filler to obtain a modified filler, then uniformly premixing the modified filler with the ultrahigh-molecular weight polyethylene, a compatilizer, an antioxidant and an additive, performing melt-extrusion, and pelleting to obtain master batches; flatly laying the master batches on a hollow mold, melting and hot-pressing the master batches in the shape of a membrane, cold-rolling, and extracting to obtain the synthetic paper. The synthetic paper prepared by the method disclosed by the invention has excellent performances of good mechanical properties, light weight, solvent resistance, micro-porosity and the like.
Description
Technical field
The invention belongs to the preparation field of synthetic paper, particularly a kind of based on ultrahigh molecular weight polyethylene the method for synthetic paper.
Background technology
Synthetic paper, also be called chemical industry film paper, plastic paper, polymer paper etc., both had as the outward appearance of natural plant fibre paper, whiteness, deflection, opaqueness, printing and writing property, had again slim and graceful, the protection against the tide, antioxygen of plastics film, the good characteristic such as acidproof, alkaline-resisting, anti-pollution concurrently.
Since the sixties in 20th century, various countries are just devoted to trial-production and the production of synthetic paper, are intended to mould Dai Mu, reduce the consumption of the forest reserves, thus protection of the environment.Nowadays, countries in the world constantly increase the demand of paper, and the vegetable fibres such as the timber of using as paper making raw material reduce day by day.
Fig. 6 is China's 2008 to 2012 paper, paper pulp and cardboard total import and export volume trend maps.
Data presentation in Fig. 6: 2008 to 2012, China's paper, paper pulp and cardboard total import value remained on 4,000,000,000 dollars of left and right, wherein increased year by year from the share of the senior printer paper of developed country's import, extraordinary paper using.Total export ascendant trend was obvious in recent years for China's paper, paper pulp and cardboard, though paper and the board product quality of outlet increase, did not break away from yet the awkward situation such as the cellulose pulp of outlet take natural resources as raw material.
At present, the production technique of domestic use mainly contains rolling process, casting method, blowing and two-way stretch method, and device fabrication line is mostly from external introduction.These methods substantially all mix paper processed by physical method by high molecular polymer, Mierocrystalline cellulose wood pulp, filler.Present stage, it is mainly that equipment requirements and production cost are relatively high that China's synthetic paper is produced the problem facing, and is the discarded environmental problem of synthetic paper on the other hand.The burning of synthetic paper can not produce objectionable impurities substantially, but now only accounts on a small quantity as the synthetic paper of waste paper recovery, and how to separate synthetic waste paper from natural waste paper is also a difficult problem.In addition, due to technical problem, in the synthetic paper of some manufacturer production of China, polymkeric substance is difficult to separate with Mierocrystalline cellulose wood pulp, polymer degradation difficulty simultaneously, and the feature of environmental protection that synthetic paper possesses can not get performance, on the contrary environment is had to certain harm.
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) resin is a kind of thermoplastic engineering plastic material of excellent combination property, it has the incomparable shock-resistance of other engineering plastics, wearability, chemical proofing, lower temperature resistance, stress cracking resistance, the anti-ability, the good low (0.936～0.964g/cm of electrical insulating property, self lubricity, density of sticking
3) etc. performance, the price of material is relatively cheap.But also there are many shortcomings in this material, as its heat-drawn wire and surface hardness low, the coefficient of expansion is large, flowing property extreme difference and forming process are very difficult.
Therefore, overcome a UHMWPE forming process difficult problem, take cheap ultrahigh molecular weight polyethylene(UHMWPE) as base material, fill a certain amount of SiO
2, TiO
2the synthetic paper of preparing light weight high-quality Deng mineral filler is a new way of synthetic paper technology of preparing.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of based on ultrahigh molecular weight polyethylene the method for synthetic paper, the synthetic paper that the method prepares has the premium propertiess such as good mechanical property, light weight, solvent resistance, many micropores.
Of the present invention a kind of based on ultrahigh molecular weight polyethylene the method for synthetic paper, comprising:
(1) mineral filler is carried out, after modification, obtain modified filler, then, with ultrahigh molecular weight polyethylene(UHMWPE), compatilizer, antioxidant, auxiliary agent, mixed in advance, melt extrude, granulation, obtains master batch; The 0-70wt% that wherein modified filler is ultrahigh molecular weight polyethylene(UHMWPE), compatilizer consumption is 1-50 times of ultrahigh molecular weight polyethylene(UHMWPE) quality, the 0.1-2wt% that antioxidant is ultrahigh molecular weight polyethylene(UHMWPE), the 0-5wt% that auxiliary dosage is ultrahigh molecular weight polyethylene(UHMWPE);
(2) above-mentioned master batch is laid in hollow mould, melting heat is pressed into membranaceous, cold rolling, and extraction, obtains synthetic paper; Wherein melting hot pressing temperature is 160-260 ℃, and pressure is 8-16MPa, and molding time is 90～180s.
In described step (1), mineral filler is SiO
2(nanometer or micron order), TiO
2(nanometer or micron order), CaCO
3, polynite, carbon black, graphite, carbon nanotube, molybdenumdisulphide, mica, kaolin, talcum powder, aluminium hydroxide, hydrated aluminum oxide, gypsum, wherein one or more of amorphous silicate, its particle diameter is nanometer, micron or grade.
In described step (1), modification is one or more that use in silane coupling agent, oleic acid, CETRIMIDE POWDER CTAB, stearic acid, the 2-20wt% that consumption is mineral filler, and the treatment time is 0.5h-5h.
In described step (1), compatilizer is whiteruss, white oil, perhydronaphthalene, paraffin oil one or more mixed solutions wherein.
In described step (1), antioxidant is antioxidant 1010: four [methyl-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, antioxidant 1076: β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid octadecyl ester, 168: three (2,4-di-tert-butyl-phenyl) phosphorous acid esters of antioxidant), antioxidant TPPI tricresyl phosphite phenylester one or more.
In described step (1), auxiliary agent is one or more in sodium stearate, calcium stearate, Magnesium Stearate.
In described step (1), melt extrude for being undertaken by single screw extrusion machine, twin screw extruder, multiple screw extruder or Banbury mixer.In described step (2), melting hot pressing is undertaken by thermocompressor or vulcanizing press.
In described step (2), extraction extraction agent used is one or more in dehydrated alcohol, methylene dichloride, dimethylbenzene, acetone.
In described step (2), extraction time is 0.1-24h.
Cold rolling in described step (2) is cold rolling 10-15min under 5-10MPa pressure.
beneficial effect
(1) synthetic paper that prepared by the present invention has the premium propertiess such as satisfactory mechanical property, light weight, solvent resistance, many micropores;
(2) it is poor that the present invention has overcome ultrahigh molecular weight polyethylene(UHMWPE) UHMWPE molten state current downflow, processes extremely difficult problem, and adopting cheap engineering plastics UHMWPE is that raw material is prepared synthetic paper;
(3) the present invention is by the selection of mineral filler kind and consumption, is expected to develop performance controlled and have a high-performance synthetic paper of special purpose;
(4) the present invention relates to the preparation process of synthetic paper simple, be easy to realize Product industrialization and produce.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of ultrahigh molecular weight polyethylene(UHMWPE) synthetic paper;
Fig. 2 is the ultrahigh molecular weight polyethylene(UHMWPE) UHMWPE synthetic paper surface SEM figure of embodiment 1; Wherein a is 1k times of SEM figure of UHMWPE synthetic paper; B is 10k times of SEM figure of UHMWPE synthetic paper;
Fig. 3 is the ultrahigh molecular weight polyethylene(UHMWPE) UHMWPE synthetic paper surface SEM figure of embodiment 2; Wherein a is 1k times of SEM figure of UHMWPE synthetic paper; B is 10k times of SEM figure of UHMWPE synthetic paper;
Fig. 4 is the ultrahigh molecular weight polyethylene(UHMWPE) UHMWPE synthetic paper surface SEM figure of embodiment 3; Wherein a is 1k times of SEM figure of UHMWPE synthetic paper; B is 10k times of SEM figure of UHMWPE synthetic paper;
Fig. 5 is the ultrahigh molecular weight polyethylene(UHMWPE) UHMWPE synthetic paper surface SEM figure of embodiment 4; Wherein a is 1k times of SEM figure of UHMWPE synthetic paper; B is 10k times of SEM figure of UHMWPE synthetic paper;
Fig. 6 is that China paper, paper pulp and cardboard total import and export volume in 2008 to 2012 are moved towards figure.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
(1) filler processing: by 20g nanometer SiO
2add the mixing solutions (V of 350ml dehydrated alcohol/water
dehydrated alcohol: V
distilled water=3:1) in, under high-shear emulsion machine, with after rotating speed 3000r/min shear agitation 20min, make nanometer SiO
2suspension is placed in three-necked bottle.In three-necked bottle, adding 34ml massfraction is that 12%(dehydrated alcohol is made thinner) Silane coupling agent KH550.Heating in water bath to 85 ℃, stirs (rotating speed is 300r/min) reaction 90min.After reaction finishes, by the suspension system suction filtration in three-necked bottle, use absolute ethanol washing filter cake, filter cake drying, grinding, obtain modified Nano SiO
2.
(2) master batch preparation: 4g modified Nano SiO
2, 16gUHMWPE, 60g white oil, 0.1g antioxidant 1010 through stirring, ultrasonic premix evenly after, extrude through twin screw extruder (four temperature setting area temperature are set to respectively 160 ℃, 200 ℃, 240 ℃, 270 ℃), then through granulator granulation.
(3) be pressed into paper: the above-mentioned master batch of 4.5g is laid in the hollow mould that 0.5mm is thick, use vulcanizing press melting heat to be pressed into membranaceous, temperature is 240 ℃, and pressure is 10MPa, and molding time is 120s.Cold rolling 15min under 5MPa pressure, takes out film to be soaked in successively each 12h in dehydrated alcohol and dichloromethane extraction liquid, obtains UHMWPE synthetic paper No. 1.
Product performance:
In table 1, data are to be quantitatively 110g/m
2enamelled paper and the performance comparison of No. 1 UHMWPE synthetic paper.
Table 1 enamelled paper and No. 1 UHMWPE synthetic paper properties contrast
Known by table 1, with respect to 110g/m
2enamelled paper, the density of UHMWPE synthetic paper is little, folding endurance and tensile strength all promote to some extent, though declines to some extent can be by interpolation TiO for whiteness
2deng method improvement.
Fig. 2 is ultrahigh molecular weight polyethylene(UHMWPE) UHMWPE synthetic paper surface SEM figure, can find out that UHMWPE synthetic paper surface is many micropores shape, and pore diameter range 0.1～5 μ m is suitable for printing.
(1) filler processing: by 20g nanometer SiO
2add the mixing solutions (V of 350ml dehydrated alcohol/water
dehydrated alcohol: V
distilled water=3:1) in, under high-shear emulsion machine, with after rotating speed 3000r/min shear agitation 20min, make nanometer SiO
2suspension is placed in three-necked bottle.In three-necked bottle, add 34ml12wt%(dehydrated alcohol to make thinner) silane coupling agent KH560.Heating in water bath to 85 ℃, stirs (rotating speed is 300r/min) reaction 90min.After reaction finishes, by the suspension system suction filtration in three-necked bottle, use absolute ethanol washing filter cake, filter cake drying, grinding, obtain modified Nano SiO
2.
(2) master batch preparation: the above-mentioned modified Nano SiO of 6g
2, 14gUHMWPE, 60g white oil, 0.1g antioxidant 1010 through stirring, ultrasonic premix evenly after, extrude granulator granulation through twin screw extruder (four temperature setting area temperature are set to respectively 160 ℃, 200 ℃, 240 ℃, 270 ℃).(3) be pressed into paper: as described in Example 1, obtain UHMWPE synthetic paper No. 2.
Product performance:
Table 2 is to being quantitatively 110g/m
2enamelled paper and No. 2 UHMWPE synthetic paper properties compare.
Table 2 enamelled paper and No. 2 UHMWPE synthetic paper properties contrasts
Known by table 2, with respect to 110g/m
2enamelled paper, the density of UHMWPE synthetic paper is little, folding endurance and tensile strength all promote to some extent, and whiteness can be by adding TiO
2deng method improvement.
Fig. 3 is UHMWPE synthetic paper surface SEM figure, can find out that UHMWPE synthetic paper surface is many micropores shape, and pore diameter range 0.1～5 μ m is suitable for printing.
Embodiment 3
(1) filler processing: by 20g nanometer SiO
2add the mixing solutions (V of 350ml dehydrated alcohol/water
dehydrated alcohol: V
distilled water=3:1) in, under high-shear emulsion machine, with after rotating speed 3000r/min shear agitation 20min, make nanometer SiO
2suspension is placed in three-necked bottle.In three-necked bottle, add 34ml12wt%(dehydrated alcohol to make thinner) silane coupling agent KH570, with dilute hydrochloric acid (dehydrated alcohol is thinner) regulate pH=4.Heating in water bath to 85 ℃, stirs (rotating speed is 300r/min) reaction 90min.After reaction finishes, by the suspension system suction filtration in three-necked bottle, use absolute ethanol washing filter cake, filter cake drying, grinding, obtain modified Nano SiO
2.
(2) master batch preparation: the above-mentioned modified Nano SiO of 8g
2, 12gUHMWPE, 60g white oil, 0.1g antioxidant 1010 through stirring, ultrasonic premix evenly after, extrude granulator granulation through twin screw extruder (four temperature setting area temperature are set to respectively 160 ℃, 200 ℃, 240 ℃, 270 ℃).
(3) be pressed into paper: as described in Example 1, obtain UHMWPE synthetic paper No. 3.
Product performance:
Table 3 is to being quantitatively 110g/m
2enamelled paper and No. 3 UHMWPE synthetic paper properties compare.
Table 3 enamelled paper and No. 3 UHMWPE synthetic paper properties contrasts
Known by table 3, with respect to 110g/m
2enamelled paper, the density of UHMWPE synthetic paper is little, folding endurance promotes to some extent, and tensile strength reduces, this and SiO
2addition is relevant.And whiteness can be by adding TiO
2deng method improvement.
Fig. 4 is UHMWPE synthetic paper surface SEM figure, can observe UHMWPE synthetic paper surface and is many micropores shape, and pore diameter range 0.1～5 μ m, is suitable for printing.
(1) master batch preparation: 20gUHMWPE, 60g white oil, 0.1g antioxidant 1010 through stirring, ultrasonic premix evenly after; extrude granulator granulation through twin screw extruder (four temperature setting area temperature are set to respectively 160 ℃, 200 ℃, 240 ℃, 270 ℃).
(2) be pressed into paper: as described in Example 1, obtain UHMWPE synthetic paper No. 4.
Product performance:
Table 4 is to being quantitatively 110g/m
2enamelled paper and No. 4 UHMWPE synthetic paper properties compare.
Table 4 enamelled paper and No. 4 UHMWPE synthetic paper properties contrasts
Known by table 4, with respect to 110g/m
2enamelled paper, the density of UHMWPE synthetic paper is little, folding endurance promotes to some extent, and tensile strength reduces, this with do not add SiO
2relevant.And whiteness can be by adding TiO
2deng method improvement.
Fig. 5 is UHMWPE synthetic paper surface SEM figure, can find out that UHMWPE synthetic paper surface is many micropores shape, pore diameter range 0.5～5 μ m, but become hole number few, can be used for printing.
Claims (10)
1. the method for synthetic paper based on ultrahigh molecular weight polyethylene, comprising:
(1) mineral filler is carried out, after modification, obtain modified filler, then mixed in advance with ultrahigh molecular weight polyethylene(UHMWPE) UHMWPE, compatilizer, antioxidant, auxiliary agent, melt extrude, granulation, obtains master batch; The 0-70wt% that wherein modified filler consumption is ultrahigh molecular weight polyethylene(UHMWPE), compatilizer consumption is 1-50 times of ultrahigh molecular weight polyethylene(UHMWPE) quality, the 0.1-2wt% that antioxidant is ultrahigh molecular weight polyethylene(UHMWPE), the 0-5wt% that auxiliary dosage is ultrahigh molecular weight polyethylene(UHMWPE);
(2) above-mentioned master batch is laid in hollow mould, melting heat is pressed into membranaceous, cold rolling, and extraction, obtains synthetic paper; Wherein melting hot pressing temperature is 160-260 ℃, and pressure is 8-16MPa, and molding time is 90～180s.
According to claim 1 a kind of based on ultrahigh molecular weight polyethylene the method for synthetic paper, it is characterized in that: mineral filler is SiO in described step (1)
2, TiO
2, CaCO
3, polynite, carbon black, graphite, carbon nanotube, molybdenumdisulphide, mica, kaolin, talcum powder, aluminium hydroxide, hydrated aluminum oxide, gypsum, wherein one or more of amorphous silicate.
According to claim 1 a kind of based on ultrahigh molecular weight polyethylene the method for synthetic paper, it is characterized in that: in described step (1), modification is one or more that use in silane coupling agent, oleic acid, CETRIMIDE POWDER CTAB, stearic acid, consumption is the 2-20wt% of mineral filler, and the treatment time is 0.5-5h.
According to claim 1 a kind of based on ultrahigh molecular weight polyethylene the method for synthetic paper, it is characterized in that: compatilizer is one or more in whiteruss, white oil, perhydronaphthalene, paraffin oil in described step (1).
According to claim 1 a kind of based on ultrahigh molecular weight polyethylene the method for synthetic paper, it is characterized in that: antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant TPPI tricresyl phosphite phenylester in described step (1).
According to claim 1 a kind of based on ultrahigh molecular weight polyethylene the method for synthetic paper, it is characterized in that: auxiliary agent is one or more in sodium stearate, calcium stearate, Magnesium Stearate in described step (1).
According to claim 1 a kind of based on ultrahigh molecular weight polyethylene the method for synthetic paper, it is characterized in that: in described step (1), melt extrude for being undertaken by single screw extrusion machine, twin screw extruder, multiple screw extruder or Banbury mixer.
According to claim 1 a kind of based on ultrahigh molecular weight polyethylene the method for synthetic paper, it is characterized in that: melting hot pressing is undertaken by thermocompressor or vulcanizing press in described step (2).
According to claim 1 a kind of based on ultrahigh molecular weight polyethylene the method for synthetic paper, it is characterized in that: cold rolling in described step (2) is cold rolling 10-15min under 5-10MPa pressure.
According to claim 1 a kind of based on ultrahigh molecular weight polyethylene the method for synthetic paper, it is characterized in that: extraction extraction agent used is one or more in dehydrated alcohol, methylene dichloride, dimethylbenzene, acetone in described step (2); Extraction time is 0.1-24h.
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Cited By (7)
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| CN104403340A (en) * | 2014-11-14 | 2015-03-11 | 无锡中洁能源技术有限公司 | Synthetic paper preparation method based on emulsion polymerization |
| CN104530537A (en) * | 2015-01-08 | 2015-04-22 | 大连塑料研究所有限公司 | Manufacturing method and forming device of high-viscosity resin boards |
| CN104592614A (en) * | 2015-01-26 | 2015-05-06 | 清华大学深圳研究生院 | Ultra-high molecular weight polyethylene composite material and preparation method thereof |
| CN105523742A (en) * | 2014-09-28 | 2016-04-27 | 杨刚 | Phosphogypsum composite material and manufacturing method thereof |
| CN105646983A (en) * | 2015-12-30 | 2016-06-08 | 东华大学 | Method for preparing printed synthetic paper based on waste plastic |
| WO2016134984A1 (en) * | 2015-02-26 | 2016-09-01 | Philips Lighting Holding B.V. | Thermally conductive composites |
| CN115286859A (en) * | 2022-08-30 | 2022-11-04 | 中国科学院兰州化学物理研究所 | Preparation method of high-damping high-wear-resistance shock insulation support friction material |
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