CN102363569B - Functional calcium carbonate for stone paper - Google Patents
Functional calcium carbonate for stone paper Download PDFInfo
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- CN102363569B CN102363569B CN 201110183021 CN201110183021A CN102363569B CN 102363569 B CN102363569 B CN 102363569B CN 201110183021 CN201110183021 CN 201110183021 CN 201110183021 A CN201110183021 A CN 201110183021A CN 102363569 B CN102363569 B CN 102363569B
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Abstract
The invention discloses functional calcium carbonate for stone paper and a preparation method thereof. The functional calcium carbonate is prepared by the following components in part by weight: 3-5 parts of glycerol, 0.5-1 part of 6-nitrobenzimidazole nitrate, 0.5-1 part of potassium nitrate, 85-95 parts of heavy calcium carbonate, 1-2 parts of barium stearate, 1-3 parts of PTFE (Polytetrafluoroethylene) micro-powder, 2-4 parts of antistatic agents, 0.4-0.6 part of bisphenol, 2-4 parts of silane coupling agents, 5-10 parts of functional monomers and 0.075-0.3 part of initiating agents. In the invention, a high-molecular interface chemical principle and the characteristics of high-molecular functionality are utilized to produce various stone paper and restrain the static generation conditions of the stone paper in the production process and the use process; and with the adoption of a softening agent, the bending resistance and the tensile strength of the paper are increased.
Description
Technical field
The present invention relates to the additive that stone paper is produced.
Background technology
Traditional technology of utilizing wood fibre papermaking causes serious environmental pollution therefrom because a large amount of consumption of natural resource, the energy reach.In order to protect national resource and environment, the various technology of human trial are improved the various drawbacks of bringing because of paper-making industry, and a kind of novel paper-making industry just is taken seriously at present---the stone paper production technology.Stone paper is take calcium carbonate as major ingredient, and add a little other organics additive, and produce through special process, reduced the consumption of timber and the pollution of water resources, and by the good name titled with environmentfriendly products, the stone paper production technology will enter a new developing period.Stone paper is a novel industry at present, and calcium carbonate is the main raw of stone paper, account for more than 80 percent of total amount, it is important process and the integral part that stone paper is produced that calcium carbonate is carried out surface modification, the various functions of stone paper also must realize by modified calcium carbonate, such as anti-electrostatic, stretch-proof and the technical features such as folding strength, flexibility.
Summary of the invention
The purpose of stone of the present invention provides a kind of functional calcium carbonate for stone paper, to satisfy the needs of relevant branch of industry.
Functional calcium carbonate for stone paper of the present invention is that the component that comprises following parts by weight prepares:
Described water-ground limestone is calcite in powder, and fineness is 1500～2500 orders, the high rising sun Chemicals of Sishui Shandong;
Static inhibitor is selected from the composition of the cruel amine of oxyethyl group bay and glyceryl monostearate, adopts the product of Dechang, Linan, Hangzhou chemistry company limited-model HDC-308,
Wherein: the cruel amine of oxyethyl group bay: the glyceryl monostearate part by weight is for respectively accounting for 50%,
Silane coupling agent is the Y-methacryloxypropyl trimethoxy silane;
The fineness of ptfe micropowder is: 2000～2500 orders;
Described functional monomer is selected from more than one in butyl acrylate, methyl acrylate, vinyl acetate or the Isooctyl acrylate monomer;
Described initiator is selected from a kind of of azo-bis-iso-dimethyl or tert butyl peroxy benzoate;
The preparation method of the functional calcium carbonate for stone paper of the present invention comprises the steps:
(a) saltpetre is dissolved in the glycerol, behind the alcohol dilution with 2 times of solution weights, adds again 6-nitrobenzimidazole nitrate, after the dissolving, 70～80 ℃ of lower reflux 1～1.5 hour;
(b) static inhibitor is mixed with silane coupling agent, and with the alcohol dilution of 2 times of mixed solution weight;
(c) in mixing kettle, add water-ground limestone and barium stearate, the product of step (a) with step (b) sprayed into respectively in the mixing kettle, add again ptfe micropowder, dihydroxyphenyl propane, be warming up to 75～85 ℃, be incubated 1～1.5 hour;
(d) with the dissolve with ethanol of initiator with 10 times of weight, then join in the functional monomer, mix, spray into again in the mixing kettle, 80～100 ℃ of lower insulations 1～2 hour, ethanol is all volatilized, obtain the stone paper functional calcium carbonate.
Functional calcium carbonate for stone paper of the present invention, it is the surface adsorption effect of utilizing calcium carbonate, by adsorbing inorganic (glycerol, 6-nitrobenzimidazole nitrate, saltpetre) and organic antistatic agents, softening agent (dihydroxyphenyl propane) and polyreaction effects on surface carry out the grafting functional group, the calcium carbonate surfactivity is increased, by adding other additives, utilize the characteristics of the macromolecule interfacial principles of chemistry and high molecular functional, after special process is processed, produce various stone paper, because the inorganic and organic antistatic agents on calcium carbonate surface and the uncompatibility of polymkeric substance, thereby to the stone paper surface transport, thereby reduced the resistance of paper surface, restrained the condition that produces static in stone paper production process and the use procedure, and softening agent anti-folding and the tensile strength of paper have been increased in stone paper.
Embodiment
Among the embodiment, if no special instructions, component is weight part.
Embodiment 1
3 parts of glycerol, 0.5 part in 6-nitrobenzimidazole nitrate, 0.5 part in saltpetre, 1 part of ptfe micropowder, 0.4 part of dihydroxyphenyl propane, 2 parts in HDC-308 static inhibitor, 90 parts of 1500 order water-ground limestones, 1 part of barium stearate, 2 parts of γ-methacryloxypropyl trimethoxy silane, 5 parts of butyl acrylates, 0.075 part of azo-bis-iso-dimethyl.
Preparation process is as follows: a. fully is dissolved in saltpetre in the glycerol, use again the alcohol dilution of 2 times of solution weights after, add again 6-nitrobenzimidazole nitrate, after the dissolving, 80 ℃ of lower reflux 1 hour; B. with static inhibitor and silane coupling agent mixes and with the alcohol dilution of 2 times of mixed solution weight; C. in mixing kettle, add water-ground limestone and barium stearate, a and b are sprayed into respectively in the mixing kettle equably, add again ptfe micropowder, dihydroxyphenyl propane, be warming up to 75 ℃, be incubated 1.5 hours; D. with the azo-bis-iso-dimethyl anhydrous alcohol solution, then all join in the butyl acrylate, fully mix, spray in the mixing kettle again, 80 ℃ of lower insulations 1 hour, and it is clean that ethanol is all volatilized, and obtains the stone paper functional calcium carbonate.
Embodiment 2
1 part in 4 parts of 6-nitrobenzimidazoles of glycerol nitrate, 0.75 part in saltpetre, 2 parts of ptfe micropowders, 0.5 part of dihydroxyphenyl propane, 3 parts in HDC-308 static inhibitor, 90 parts of 1800 order water-ground limestones, 1.5 parts of barium stearates, 3 parts of γ-methacryloxypropyl trimethoxy silane, 6 parts of methyl acrylates, 0.12 part of tert butyl peroxy benzoate.
Preparation process is as follows: a. fully is dissolved in saltpetre in the glycerol, use again the alcohol dilution of 2 times of solution weights after, add again 6-nitrobenzimidazole nitrate, fully after the dissolving, 70 ℃ of lower reflux 1.5 hours; B. with static inhibitor and silane coupling agent mixes and with the alcohol dilution of 2 times of mixed solution weight; C. in mixing kettle, add water-ground limestone and barium stearate, a and b are sprayed into respectively in the mixing kettle equably, add again ptfe micropowder, dihydroxyphenyl propane, be warming up to 80 ℃, be incubated 1.5 hours; D. with the tert butyl peroxy benzoate anhydrous alcohol solution, then all join in the methyl acrylate, mix, spray in the mixing kettle again, 90 ℃ of lower insulations 1.5 hours, and it is clean that ethanol is all volatilized, and obtains the stone paper functional calcium carbonate.
Embodiment 3
5 parts of glycerol, 0.75 part in 6-nitrobenzimidazole nitrate, 1 part in saltpetre, 3 parts of ptfe micropowders, 0.6 part of dihydroxyphenyl propane, 4 parts in HDC-308 static inhibitor, 95 parts of 2200 order water-ground limestones, 2 parts of barium stearates, 4 parts of γ-methacryloxypropyl trimethoxy silane, 7 parts of vinyl acetates, 0.15 part of azo-bis-iso-dimethyl.
Preparation process is as follows: a. fully is dissolved in saltpetre in the glycerol, use again the alcohol dilution of 2 times of solution weights after, add again 6-nitrobenzimidazole nitrate, after the dissolving, 75 ℃ of lower reflux 1.5 hours; B. with static inhibitor and silane coupling agent mixes and with the alcohol dilution of 2 times of mixed solution weight; C. in mixing kettle, add water-ground limestone and barium stearate, a and b are sprayed into respectively in the mixing kettle, add again ptfe micropowder, dihydroxyphenyl propane, be warming up to 85 ℃, be incubated 1.5 hours; D. with the azo-bis-iso-dimethyl anhydrous alcohol solution, then all join in the vinyl acetate, fully mix, spray in the mixing kettle again, 85 ℃ of lower insulations 2 hours, and it is clean that ethanol is all volatilized, and obtains the stone paper functional calcium carbonate.
Embodiment 4
3 parts of glycerol, 1 part in 6-nitrobenzimidazole nitrate, 0.5 part in saltpetre, 1 part of ptfe micropowder, 0.4 part of dihydroxyphenyl propane, 2 parts in HDC-308 static inhibitor, 85 parts of 2500 order water-ground limestones, 1 part of barium stearate, 2 parts of γ-methacryloxypropyl trimethoxy silane, 8 parts of Isooctyl acrylate monomers, 0.2 part of tert butyl peroxy benzoate.
Preparation process is as follows: a. is dissolved in saltpetre in the glycerol, use again the alcohol dilution of 2 times of solution weights after, add again 6-nitrobenzimidazole nitrate, after the dissolving, 80 ℃ of lower reflux 1 hour; B. with static inhibitor and silane coupling agent mixes and with the alcohol dilution of 2 times of mixed solution weight; C. in mixing kettle, add water-ground limestone and barium stearate, a and b are sprayed into respectively in the mixing kettle, add again ptfe micropowder, dihydroxyphenyl propane, be warming up to 75 ℃, be incubated 1 hour; D. with the tert butyl peroxy benzoate anhydrous alcohol solution, then all join in the Isooctyl acrylate monomer, fully mix, spray into again in the mixing kettle, 95 ℃ of lower insulations 2 hours, and it is clean that ethanol is all volatilized, and obtains the stone paper functional calcium carbonate.
Embodiment 5
4 parts of glycerol, 0.75 part in 6-nitrobenzimidazole nitrate, 0.75 part in saltpetre, 2 parts of ptfe micropowders, 0.5 part of dihydroxyphenyl propane, 3 parts in HDC-308 static inhibitor, 90 parts of 2000 order water-ground limestones, 1.5 parts of barium stearates, 3 parts of γ-methacryloxypropyl trimethoxy silane, 3 parts of butyl acrylates, 3 parts of Isooctyl acrylate monomers, 3 parts of methyl acrylates, 0.25 part of azo-bis-iso-dimethyl,
Preparation process is as follows: a. is dissolved in saltpetre in the glycerol, use again the alcohol dilution of 2 times of solution weights after, add again 6-nitrobenzimidazole nitrate, after the dissolving, 70 ℃ of lower reflux 1.5 hours; B. with static inhibitor and silane coupling agent mixes and with the alcohol dilution of 2 times of mixed solution weight; C. in mixing kettle, add water-ground limestone and barium stearate, a and b are sprayed into respectively in the mixing kettle, add again ptfe micropowder, dihydroxyphenyl propane, be warming up to 80 ℃, be incubated 1 hour; D. the azo-bis-iso-dimethyl dissolve with ethanol joins in butyl acrylate and Isooctyl acrylate monomer and the methyl acrylate mixed solution, fully mixes, spray into again in the mixing kettle, 85 ℃ of lower insulations 1 hour, and it is clean that ethanol is all volatilized, and obtains the stone paper functional calcium carbonate.
Embodiment 6
5 parts of glycerol, 0.5 part in 6-nitrobenzimidazole nitrate, 1 part in saltpetre, 3 parts of ptfe micropowders, 0.6 part of dihydroxyphenyl propane, 4 parts in HDC-308 static inhibitor, 95 parts of 2500 order water-ground limestones, 2 parts of barium stearates, 4 parts of γ-methacryloxypropyl trimethoxy silane, 2.5 parts of butyl acrylates, 2.5 parts of Isooctyl acrylate monomers, 2.5 parts of methyl acrylates, 2.5 parts of vinyl acetates, 0.3 part of tert butyl peroxy benzoate
Preparation process is as follows: a. fully is dissolved in saltpetre in the glycerol, use again the alcohol dilution of 2 times of solution weights after, add again 6-nitrobenzimidazole nitrate, after the dissolving, 75 ℃ of lower reflux 1.5 hours; B. with static inhibitor and silane coupling agent mixes and with the alcohol dilution of 2 times of mixed solution weight; C. in mixing kettle, add water-ground limestone and barium stearate, a and b are sprayed into respectively in the mixing kettle, add again ptfe micropowder, dihydroxyphenyl propane, be warming up to 85 ℃, be incubated 1 hour; D. tert butyl peroxy benzoate dissolve with ethanol, join in the mixed solution of butyl acrylate, Isooctyl acrylate monomer, methyl acrylate and vinyl acetate, fully mix, spray into again in the mixing kettle, 100 ℃ of lower insulations 1 hour, and it is clean that ethanol is all volatilized, and obtains the stone paper functional calcium carbonate.
Embodiment 7
By following test function is carried out to functional calcium carbonate that application test measures: 90 parts of functional calcium carbonates, 15 parts of linear low density polyethylenes, 10 parts of hot melt adhesives, 1.5 parts of erucicamides, 0.5 part of stearic acid, 1.5 parts of epoxy tetrahydro-2-ethylhexyl phthalates, 1.5 parts of dioctyl sebacates, 0.6 part of polyethylene wax, 1 part of Span60.
Described hot melt adhesive is the ethylene-vinyl acetate copolymer type, is called for short EVA, 85～120 ℃ of fusing points; Preferred 120 ℃;
Described polyethylene wax is polyamide modified polyethylene micropowder wax, and adopting the Clariant company trade mark is the product of 9615A;
Stone paper is warming up to 160 ℃ with functional calcium carbonate, add again linear low density polyethylene, hot melt adhesive, epoxy tetrahydro-2-ethylhexyl phthalate, modified polyethylene wax, erucicamide, Span60, mix and blend 60 minutes, then send into 182 ℃ of plasticizing machine plasticizings, 182 ℃ of forcing machine curtain coatings, 182 ℃ of four axle rolling press is rolled into the stone paper of 0.08mm, after the cooling, through 25 ± 2 ℃, rolling is packed after relative humidity 60 ± 2% balances again.
Testing method: because of the stone paper of packing aspect temporarily without national standard, can only be take wrapping paper as measuring relevant data with reference to the method with reference to national sector standard QB 1313-1991 (People's Republic of China's industry standard), and in conjunction with the performance of wrapping paper actual operation requirements, carry out practical measurement with reference to the existing antistatic paper product of actual packaging in market.
The contrast sample is commercially available antistatic kraft paper.
Can judge from determination data; The various functions index of functional calcium carbonate of the present invention in stone paper is produced reaches technical requirements, and functions calcium carbonate is the good functional material of production stone paper.
Claims (3)
1. being used for the functional calcium carbonate of stone paper, it is characterized in that, is that the component that comprises following parts by weight prepares:
Described functional monomer is selected from more than one in butyl acrylate, methyl acrylate, vinyl acetate or the Isooctyl acrylate monomer;
The preparation method of described functional calcium carbonate for stone paper is characterized in that, comprises the steps:
(a) saltpetre is dissolved in the glycerol, behind the alcohol dilution with 2 times of solution weights, adds again 6-nitrobenzimidazole nitrate, after the dissolving, 70～80 ℃ of lower reflux 1～1.5 hour;
(b) static inhibitor is mixed with silane coupling agent, and with the alcohol dilution of 2 times of mixed solution weight;
(c) in mixing kettle, add water-ground limestone and barium stearate, the product of step (a) with step (b) sprayed into respectively in the mixing kettle, add again ptfe micropowder, dihydroxyphenyl propane, be warming up to 75～85 ℃, be incubated 1～1.5 hour;
(d) with the dissolve with ethanol of initiator with 10 times of weight, then join in the functional monomer, mix, spray into again in the mixing kettle, 80～100 ℃ of lower insulations 1～2 hour, ethanol is all volatilized, obtain the stone paper functional calcium carbonate.
2. the functional calcium carbonate for stone paper according to claim 1 is characterized in that, static inhibitor is selected from the composition of the cruel amine of oxyethyl group bay and glyceryl monostearate.
3. the functional calcium carbonate for stone paper according to claim 1 and 2 is characterized in that, described initiator is selected from a kind of in azo-bis-iso-dimethyl or the tert butyl peroxy benzoate.
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| CN 201110183021 CN102363569B (en) | 2011-06-30 | 2011-06-30 | Functional calcium carbonate for stone paper |
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| CN102363569B true CN102363569B (en) | 2013-03-20 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102849985A (en) * | 2012-09-19 | 2013-01-02 | 重庆五明科技有限责任公司 | Environment-friendly stone paper and preparation method thereof |
| CN104533040A (en) * | 2014-12-17 | 2015-04-22 | 邱有英 | Manufacture method for attapulgite stone paper wallpaper |
| CN107474311B (en) * | 2017-08-17 | 2018-08-03 | 张家界荣丰新材料有限公司 | A kind of preparation method of rubber industry agstone |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL314854A1 (en) * | 1993-12-10 | 1996-09-30 | Minerals Technologies | Method of treating an inorganic paper filler with polysacharides |
| CN101134852A (en) * | 2007-10-15 | 2008-03-05 | 江苏河海纳米科技股份有限公司 | Inorganic powder organic surface modifying method |
| CN101704661A (en) * | 2009-11-18 | 2010-05-12 | 蔡茂友 | Method for preparing raw material for making paper by using stone |
| CN101831835A (en) * | 2010-05-01 | 2010-09-15 | 陈美章 | Stone papermaking method |
| CN101871182A (en) * | 2010-06-18 | 2010-10-27 | 成都新柯力化工科技有限公司 | Thermoplasticity environmentally-friendly stone paper and preparation method |
-
2011
- 2011-06-30 CN CN 201110183021 patent/CN102363569B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL314854A1 (en) * | 1993-12-10 | 1996-09-30 | Minerals Technologies | Method of treating an inorganic paper filler with polysacharides |
| CN101134852A (en) * | 2007-10-15 | 2008-03-05 | 江苏河海纳米科技股份有限公司 | Inorganic powder organic surface modifying method |
| CN101704661A (en) * | 2009-11-18 | 2010-05-12 | 蔡茂友 | Method for preparing raw material for making paper by using stone |
| CN101831835A (en) * | 2010-05-01 | 2010-09-15 | 陈美章 | Stone papermaking method |
| CN101871182A (en) * | 2010-06-18 | 2010-10-27 | 成都新柯力化工科技有限公司 | Thermoplasticity environmentally-friendly stone paper and preparation method |
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Effective date of registration: 20141127 Address after: 273200 Shandong Province Economic Development Zone Jining city Surabaya County Springs Road Patentee after: Surabaya Gao Xuxin Material Co., Ltd. Address before: 200223 room 1, building 388, No. 701, Xuhui District, Shanghai, Tianlin Road Patentee before: Shanghai Dongsheng new material Co., Ltd. |