CN102212223B - Manufacture method for composite environmentally-friendly paper - Google Patents
Manufacture method for composite environmentally-friendly paper Download PDFInfo
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- CN102212223B CN102212223B CN2011101065264A CN201110106526A CN102212223B CN 102212223 B CN102212223 B CN 102212223B CN 2011101065264 A CN2011101065264 A CN 2011101065264A CN 201110106526 A CN201110106526 A CN 201110106526A CN 102212223 B CN102212223 B CN 102212223B
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- calcium carbonate
- sheet material
- carbonate crystal
- crystal whisker
- modification
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Abstract
The invention relates to a manufacture method for composite environmentally-friendly paper, and the method is characterized by comprising the following steps: firstly modifying calcium carbonate crystal whiskers, adding high-density polyethylene, the modified calcium carbonate crystal whiskers, anhydrous calcium chloride, sodium dodecylbenzene sulfonate and antioxidant 1076 to an internal mixer, and carrying out internal mixing until the temperature is 150-180 DEG C; conveying the internal-mixed material to an extruder, conveying an extruded melt to a calender by a virtue of T-shaped die head, and calendering at the temperature of 140-160 DEG C to obtain sheets; cooling the sheets to below 50 DEG C by utilizing air with the relative humidity of 50-100%; and conveying the cooled sheets to a multi-roller stretcher, preheating the sheets to 110-130 DEG C, and stretching by virtue of 2-5 groups of stretching rollers to obtain the required environmentally-friendly paper. The environmentally-friendly paper acquired by using the method provided by the invention has the density of 0.6-1.2 g/cm<3>.
Description
Technical field
The present invention relates to a kind of method of manufacture of composite environmental-friendly paper.
Background technology
General whisker price is higher, has limited its application in plastics industry, and lime carbonate (CaCO
3) whisker is the staple fibre of length 20～30 μ m, diameter 0.5～3.0 μ m; Production technique is simple; Cheap, harmless, be the huge inorganic crystal whisker of development potentiality; Can be used for plastics strengthen, toughness reinforcing, improve plastics thermostability and surface smoothness, be rising type material.
Environmental protection paper, past attempts are called as chemical industry film paper, plastic paper, polymer paper.It is to be main raw material with lime carbonate and high molecular polymer, handles through " paper shape position ", and that processes is similar with common plant fiber paper in appearance, on performance than its more superior a kind of new type of paper.Environmental protection paper is a kind of plastic material novel product, through various The application of new technique, makes it have the characteristic of plastics and paper simultaneously.The production process of environmental protection paper is pollution-free, can reclaim, and recycle is a major reform of modern paper production.As novel paper kind, the premium properties of environmental protection paper is more and more obvious, and purposes also more and more widely has been extended to many frontiers, and many product innovations constantly are developed.
Chinese invention patent CN101618622 discloses a kind of plastic synthetic paper, is made up of inside and outside layer and middle layer, and the raw material and the weight percent of said inside and outside layer are CaCO
325～35%, low-tension wire property polyethylene 35%～45%, imitative paper masterbatch 20%～30% and white master material 10%～20%, the raw material in said middle layer and weight percent are linear low density polyethylene 40%～70%, CaCO320%～50% and white master material 10%～20%.
Chinese invention patent CN101659770 provides a kind of flame-retardant synthetic paper.Comprise acrylic resin, polyvinyl resin, inorganic fillings, coupling agent, static inhibitor, lubricant, tinting material.Each raw material and parts by weight thereof are: acrylic resin 100%, polyvinyl resin 20～90%, inorganic fillings 50～300%, coupling agent 1～8%, static inhibitor 1～5%, lubricant 0.5～5%, tinting material 5～20%, fire retardant 5～35%.Each raw material of this flame-retardant synthetic paper through mixing, mixing gel, rolling press moulding, doff roll draw, embossed, again through cooling, corona treatment, rolling product.
Chinese invention patent CN101747567A relates to a kind of novel PS alloy synthetic paper that had both improved deflection, surface polarity and surface hardness and resistance to chemical attack; Through extruding the paper of casting method moulding; Outward appearance is white and opaque; With good rerum natura and splendid price, can replace current art paper commonly used, substitute product with compound PE of general paper and the compound BOPP film of general paper; Be applied to general printed matter and processed goods with waterproof, the characteristics of cannot not tearing brokenly; Need to be applied to permanent data of preserving with the good characteristic of weathering resistance, to be adapted to the label of the packing of various carafes, jar.
Chinese invention patent CN101676326 provides a kind of composition and preparation method of novel synthetic paper material.By 50～85% (weight percent) polyolefin blends; The oxidation inhibitor elder generation premix of aforementioned material gross weight meter 0.1～1% is formed and added to 10% (weight percent) inorganic mineral powder and 5%～12% (weight percent) auxiliary agent; Through the twin screw extruder extruding pelletization, process the high-rigidity high-ductility base resin again, simultaneously through adding auxiliary agent (static inhibitor, antiseptic-germicide, perfuming agent etc.); Evenly spread in the resin matrix through melt blending, can satisfy the difference in functionality demand.
Chinese invention patent CN101760990A provides papermaking material, preparation method and the papermaking process thereof of environmental protection synthetic paper.Material is made up of modified mineral fiber, thermoplastic starch, derivatived cellulose, compatilizer, ancillary component etc.Wherein the modified mineral fiber is the mineral fibre through fibrosis superfine grinding and surface recombination modified processing of 5～10 microns of median sizes and length 8～15/1; Thermoplastic starch is that ancillary component comprises lubricant and tinting material through the starch of miniaturization and plasticization and modification processing.The preparation of this papermaking material is with behind each material composition thorough mixing successively, obtains with the screw extruder extruding pelletization in 60 ℃～180 ℃.By the plastic working mode this material is carried out two-way stretch with calendering or the blowing of paper film machine and promptly may be made in corresponding paper product.
The present invention adopts calcium carbonate crystal whisker modification and high density polyethylene(HDPE) to make the environmental protection Composite Paper; Strengthened the bonding force between calcium carbonate crystal whisker and the high density polyethylene(HDPE) through the modified calcium carbonate whisker; Calcium carbonate crystal whisker is fibrous can playing as the effect of traditional paper fiber-like, and the support that interweaves of traditional paper fiber makes paper that certain deflection arranged.And if the environmental protection Composite Paper draw ratio that does not add filamentary material is greatly will deflection lower, the little then paper density of draw ratio is big, keeps certain deflection in order to reach bigger draw ratio, and calcium carbonate crystal whisker is a kind of more satisfactory selection.
Summary of the invention
The method of manufacture of a kind of composite environmental-friendly paper of the present invention; It is characterized in that: earlier with the calcium carbonate crystal whisker modification; The method of modification is: in weight part the triethylamine of 1 part chelating titanate coupling agent and 0.5 part being mixed and process the chelating titanate quaternary ammonium salt, the quaternary ammonium salt that makes is distributed in 600 parts the water, is that 25～50 μ m, mean diameter are that the calcium carbonate crystal whisker of 1～3 μ m is distributed in the above-mentioned water for 100～200 parts with mean length again; Stirred 30～60 minutes; Filter, filter cake obtains the calcium carbonate crystal whisker of modification 100～120 ℃ of oven dry down; Calcium carbonate crystal whisker, Calcium Chloride Powder Anhydrous, X 2073, the antioxidant 1076 of high density polyethylene(HDPE), modification are joined in the Banbury mixer, reach 150～180 ℃ through banburying to temperature; Then the material after the banburying is sent in the forcing machine, melt extrusion is sent in the rolling press through the T die, prolongs into sheet material 140～160 ℃ temperatures; It is below 50～100% the air cooling to 50 ℃ that sheet material that rolling press comes out uses relative humidity; Then sheet material is sent in the multiple roll drawing machine, sheet material is preheated to 110～130 ℃ earlier, stretches through 2～5 groups of draw rolls, obtains the environmental protection paper that needs.
Described high density polyethylene(HDPE) by weight is that 20～35 parts, the calcium carbonate crystal whisker of modification are that 65～80 parts, Calcium Chloride Powder Anhydrous are that 0.3～1.5 part, X 2073 are that 0.2～1.0 part, antioxidant 1076 are 0.1～0.5 part.
The heat fusing flow index MFI of described high density polyethylene(HDPE) is less than 1.0.
Described chelating titanate coupling agent is one or more in two (stearyl-) ethylene titanic acid ester, two (dioctylphosphoric acid ester) ethylene titanic acid ester.
The draw ratio of described sheet material in the multiple roll drawing machine is 2.5～4.5.
The density of described composite environmental-friendly paper is 0.6～1.2g/cm
3
Embodiment
Embodiment 1
0.5kg two (stearyl-) ethylene titanic acid ester and 0.25kg triethylamine mixed process the chelating titanate quaternary ammonium salt; The quaternary ammonium salt that makes is distributed in the water of 480kg; Be that 25 μ m, mean diameter are that the calcium carbonate crystal whisker of 1 μ m is distributed in the above-mentioned water with the 80kg mean length again, stirred 30 minutes, filter; Filter cake obtains the calcium carbonate crystal whisker of 74kg modification 100 ℃ of oven dry down; With heat fusing flow index MFI is that 0.3 high density polyethylene(HDPE) 26kg, the calcium carbonate crystal whisker 74kg of modification, Calcium Chloride Powder Anhydrous 1.0kg, X 2073 0.5kg, antioxidant 1076 0.1kg join in the Banbury mixer; When banburying to temperature reaches 180 ℃, stop banburying; Material after the banburying is sent in the forcing machine, and the extrusion temperature of forcing machine is 200 ℃, and melt extrusion is sent in the rolling press through the T die, prolongs into sheet material 150 ℃ temperatures, and the thickness of sheet material is 190 μ m, and width is 800mm; It is 50% air cooling to 30 ℃ that sheet material that rolling press comes out uses relative humidity; Then sheet material is sent in the multiple roll drawing machine, sheet material is preheated to 124 ℃ through oily warming mill earlier in drawing machine, stretches through 4 groups of draw rolls, and draw ratio is 4.2, and the composite environmental-friendly paper density that obtains is 0.7g/cm
3
Embodiment 2
0.8kg two (dioctylphosphoric acid ester) ethylene titanic acid ester and 0.4kg triethylamine mixed process the chelating titanate quaternary ammonium salt; The quaternary ammonium salt that makes is distributed in the water of 400kg; Be that 50 μ m, mean diameter are that the calcium carbonate crystal whisker of 3 μ m is distributed in the above-mentioned water with the 85kg mean length again, stirred 60 minutes, filter; Filter cake obtains the calcium carbonate crystal whisker of 80kg modification 120 ℃ of oven dry down; With heat fusing flow index MFI is that 0.8 high density polyethylene(HDPE) 20kg, the calcium carbonate crystal whisker 80kg of modification, Calcium Chloride Powder Anhydrous 1.2kg, X 2073 0.2kg, antioxidant 1076 0.5kg join in the Banbury mixer; When banburying to temperature reaches 175 ℃, stop banburying; Material after the banburying is sent in the forcing machine, and the extrusion temperature of forcing machine is 200 ℃, and melt extrusion is sent in the rolling press through the T die, prolongs into sheet material 155 ℃ temperatures, and the thickness of sheet material is 180 μ m, and width is 800mm; It is 100% air cooling to 45 ℃ that sheet material that rolling press comes out uses relative humidity; Then sheet material is sent in the multiple roll drawing machine, sheet material is preheated to 128 ℃ through oily warming mill earlier in drawing machine, stretches through 5 groups of draw rolls, and draw ratio is 4.5, and the composite environmental-friendly paper density that obtains is 0.6g/cm
3
Embodiment 3
0.6kg two (dioctylphosphoric acid ester) ethylene titanic acid ester and 0.3kg triethylamine mixed process the chelating titanate quaternary ammonium salt; The quaternary ammonium salt that makes is distributed in the water of 700kg; Be that 40 μ m, mean diameter are that the calcium carbonate crystal whisker of 2 μ m is distributed in the above-mentioned water with the 75kg mean length again, stirred 50 minutes, filter; Filter cake obtains the calcium carbonate crystal whisker of 70kg modification 115 ℃ of oven dry down; With heat fusing flow index MFI is that 0.08 high density polyethylene(HDPE) 30kg, the calcium carbonate crystal whisker 70kg of modification, Calcium Chloride Powder Anhydrous 1.5kg, X 2073 0.4kg, antioxidant 1076 0.4kg join in the Banbury mixer; When banburying to temperature reaches 150 ℃, stop banburying; Material after the banburying is sent in the forcing machine, and the extrusion temperature of forcing machine is 200 ℃, and melt extrusion is sent in the rolling press through the T die, prolongs into sheet material 150 ℃ temperatures, and the thickness of sheet material is 140 μ m, and width is 800mm; It is 90% air cooling to 50 ℃ that sheet material that rolling press comes out uses relative humidity; Then sheet material is sent in the multiple roll drawing machine, sheet material is preheated to 120 ℃ through oily warming mill earlier in drawing machine, stretches through 2 groups of draw rolls, and draw ratio is 2.5, and the composite environmental-friendly paper density that obtains is 1.2g/cm
3
Embodiment 4
0.7kg two (stearyl-) ethylene titanic acid ester and 0.35kg triethylamine mixed process the chelating titanate quaternary ammonium salt; The quaternary ammonium salt that makes is distributed in the water of 480kg; Be that 35 μ m, mean diameter are that the calcium carbonate crystal whisker of 2 μ m is distributed in the above-mentioned water with the 75kg mean length again, stirred 40 minutes, filter; Filter cake obtains the calcium carbonate crystal whisker of 69kg modification 110 ℃ of oven dry down; With heat fusing flow index MFI is that 0.7 high density polyethylene(HDPE) 31kg, the calcium carbonate crystal whisker 69kg of modification, Calcium Chloride Powder Anhydrous 0.3kg, X 2073 0.2kg, antioxidant 1076 0.3kg join in the Banbury mixer; When banburying to temperature reaches 165 ℃, stop banburying; Material after the banburying is sent in the forcing machine, and the extrusion temperature of forcing machine is 200 ℃, and melt extrusion is sent in the rolling press through the T die, prolongs into sheet material 158 ℃ temperatures, and the thickness of sheet material is 130 μ m, and width is 800mm; It is 80% air cooling to 35 ℃ that sheet material that rolling press comes out uses relative humidity; Then sheet material is sent in the multiple roll drawing machine, sheet material is preheated to 117 ℃ through oily warming mill earlier in drawing machine, stretches through 3 groups of draw rolls, and draw ratio is 3.0, and the composite environmental-friendly paper density that obtains is 1.0g/cm
3
Embodiment 5
0.8kg two (stearyl-) ethylene titanic acid ester and 0.4kg triethylamine mixed process the chelating titanate quaternary ammonium salt; The quaternary ammonium salt that makes is distributed in the water of 350kg; Be that 30 μ m, mean diameter are that the calcium carbonate crystal whisker of 1 μ m is distributed in the above-mentioned water with the 70kg mean length again, stirred 45 minutes, filter; Filter cake obtains the calcium carbonate crystal whisker of 66kg modification 113 ℃ of oven dry down; With heat fusing flow index MFI is that 0.05 high density polyethylene(HDPE) 34kg, the calcium carbonate crystal whisker 66kg of modification, Calcium Chloride Powder Anhydrous 0.7kg, X 2073 0.8kg, antioxidant 1076 0.5kg join in the Banbury mixer; When banburying to temperature reaches 172 ℃, stop banburying; Material after the banburying is sent in the forcing machine, and the extrusion temperature of forcing machine is 200 ℃, and melt extrusion is sent in the rolling press through the T die, prolongs into sheet material 151 ℃ temperatures, and the thickness of sheet material is 165 μ m, and width is 800mm; It is 85% air cooling to 45 ℃ that sheet material that rolling press comes out uses relative humidity; Then sheet material is sent in the multiple roll drawing machine, sheet material is preheated to 127 ℃ through oily warming mill earlier in drawing machine, stretches through 4 groups of draw rolls, and draw ratio is 4.0, and the composite environmental-friendly paper density that obtains is 0.7g/cm
3
Claims (4)
1. the method for manufacture of a composite environmental-friendly paper; It is characterized in that: earlier with the calcium carbonate crystal whisker modification; The method of modification is: in weight part the triethylamine of 1 part chelating titanate coupling agent and 0.5 part being mixed and process the chelating titanate quaternary ammonium salt, the quaternary ammonium salt that makes is distributed in 600 parts the water, is that 25～50 μ m, mean diameter are that the calcium carbonate crystal whisker of 1～3 μ m is distributed in the above-mentioned water for 100～200 parts with mean length again; Stirred 30～60 minutes; Filter, filter cake obtains the calcium carbonate crystal whisker of modification 100～120 ℃ of oven dry down; Calcium carbonate crystal whisker, Calcium Chloride Powder Anhydrous, X 2073, the antioxidant 1076 of high density polyethylene(HDPE), modification are joined in the Banbury mixer, reach 150～180 ℃ through banburying to temperature; Then the material after the banburying is sent in the forcing machine, melt extrusion is sent in the rolling press through the T die, prolongs into sheet material 140～160 ℃ temperatures; It is below 50～100% the air cooling to 50 ℃ that sheet material that rolling press comes out uses relative humidity; Then sheet material is sent in the multiple roll drawing machine, sheet material is preheated to 110～130 ℃ earlier, through 2～5 groups of stretchings, obtains the environmental protection paper that needs;
Above-mentioned described method, wherein high density polyethylene(HDPE) is that 20～35 parts, the calcium carbonate crystal whisker of modification are that 65～80 parts, Calcium Chloride Powder Anhydrous are that 0.3～1.5 part, X 2073 are that 0.2～1.0 part, antioxidant 1076 are 0.1～0.5 part by weight.
2. the described method of claim 1, wherein the chelating titanate coupling agent is one or more in two (stearyl-) ethylene titanic acid ester, two (dioctylphosphoric acid ester) ethylene titanic acid ester.
3. the described method of claim 1, wherein the draw ratio of sheet material in the multiple roll drawing machine is 2.5～4.5.
4. the described method of claim 1, the density of wherein resulting composite environmental-friendly paper is 0.6～1.2g/cm
3
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| CN2011101065264A CN102212223B (en) | 2011-04-27 | 2011-04-27 | Manufacture method for composite environmentally-friendly paper |
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| CN2011101065264A CN102212223B (en) | 2011-04-27 | 2011-04-27 | Manufacture method for composite environmentally-friendly paper |
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| CN102212223B true CN102212223B (en) | 2012-11-14 |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634847B (en) * | 2012-04-25 | 2015-04-22 | 昆明理工大学 | Method for surface modification of calcium sulfate crystal whisker |
| CN102838768B (en) * | 2012-09-26 | 2013-12-25 | 华东理工大学 | Method for improving strength and surface absorptivity of synthetic paper |
| CN102838796B (en) * | 2012-09-26 | 2014-02-12 | 华东理工大学 | Method for preparing synthetic paper with porous surface |
| CN104448504B (en) * | 2014-12-29 | 2017-02-22 | 华东理工大学 | Manufacturing method of wood fiber composite environment-friendly paper |
| CN104558774B (en) * | 2014-12-29 | 2016-10-05 | 华东理工大学 | A kind of polyacrylonitrile fibre strengthens the method that height fills environment protecting paper |
| CN104530534B (en) * | 2014-12-29 | 2017-01-11 | 华东理工大学 | Method for enhancing high-fill synthetic paper strength through wood fibers |
| CN104448507B (en) * | 2014-12-29 | 2017-01-11 | 华东理工大学 | Method for using polypropylene fiber for enhancing highly-filled environment-friendly paper |
| CN104631199B (en) * | 2015-01-28 | 2016-07-20 | 陕西科技大学 | A kind of aramid paper adding potassium titanate crystal whisker and preparation method thereof |
| CN104631200B (en) * | 2015-01-28 | 2016-09-14 | 陕西科技大学 | A kind of polyimide fiber paper adding potassium titanate crystal whisker and preparation method thereof |
| CN104875367A (en) * | 2015-06-16 | 2015-09-02 | 华东理工大学 | Method for preparing environmentally-friendly synthetic paper through two-way stretching machine |
| CN104861274B (en) * | 2015-06-16 | 2017-01-11 | 华东理工大学 | Calendaring preparation method for environment-friendly paper from paper mill sludge |
| CN104861275B (en) * | 2015-06-16 | 2017-03-08 | 华东理工大学 | A kind of method of environmental protection synthetic paper preparation |
| CN109111762A (en) * | 2018-10-09 | 2019-01-01 | 河南骏化发展股份有限公司 | A kind of preparation method of ink modified nano calcium carbonate |
| CN113879681A (en) * | 2021-08-23 | 2022-01-04 | 箱联天下供应链管理有限公司 | Bamboo-plastic new material integrated tray turnover box |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760990A (en) * | 2009-12-17 | 2010-06-30 | 成都新柯力化工科技有限公司 | Paper making material, preparation method and paper making method of environment-friendly synthetic paper |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20030089450A1 (en) * | 2001-11-06 | 2003-05-15 | Lin Allen Fong-Chin | Manufacturing method for improving the yield and production rate of biaxial-oriented polypropylene pearly synthetic paper |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760990A (en) * | 2009-12-17 | 2010-06-30 | 成都新柯力化工科技有限公司 | Paper making material, preparation method and paper making method of environment-friendly synthetic paper |
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