WO2023050259A1 - 一种薄膜及其制备方法 - Google Patents
一种薄膜及其制备方法 Download PDFInfo
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- WO2023050259A1 WO2023050259A1 PCT/CN2021/122051 CN2021122051W WO2023050259A1 WO 2023050259 A1 WO2023050259 A1 WO 2023050259A1 CN 2021122051 W CN2021122051 W CN 2021122051W WO 2023050259 A1 WO2023050259 A1 WO 2023050259A1
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- WO
- WIPO (PCT)
- Prior art keywords
- calcium carbonate
- mesh
- film
- weight ratio
- masterbatch
- Prior art date
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- 239000010409 thin film Substances 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 62
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 29
- 239000010408 film Substances 0.000 claims abstract description 22
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000004698 Polyethylene Substances 0.000 claims abstract description 12
- -1 polyethylene Polymers 0.000 claims abstract description 11
- 229920000573 polyethylene Polymers 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 238000005266 casting Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims abstract description 5
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 5
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 5
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 5
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000003205 fragrance Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
Classifications
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
Definitions
- the invention relates to the technology in the field of polyolefin films, in particular to a film with a high filling content of calcium carbonate, certain mechanical properties and suitable for preparation at high stretching rates.
- the filling amount of calcium carbonate is low, resulting in high cost, and there are also more fillings, such as CN102875869, which has a high calcium carbonate content, but PE can only be cast into a film by stretching, and through low
- the mechanical properties of the film prepared at a stretching rate are lower than those at a high stretching rate, and the two-step blending and extrusion method is used, and the preparation process is more complicated. Therefore, how to provide a film with high calcium carbonate filling content, good mechanical properties and simple manufacturing process is very necessary.
- the present invention provides a kind of following technical scheme:
- a film the film is prepared from the following raw materials in parts by weight: substrate 35-48%, surface-modified calcium carbonate filler 49-51%, and the rest are additives;
- the base material is EVA, LDPE and LLDPE with a weight ratio of 1:(4 ⁇ 9):(1 ⁇ 4), and the calcium carbonate includes a particle size range of Three kinds of calcium carbonate particles of 2000-4000 mesh, 4000-6000 mesh, 6000-8000 mesh and 1-100nm, the weight ratio is (5-10): (6-11): (7-12): (1-2 ), and the content of the four kinds of calcium carbonate is 6000-8000 mesh calcium carbonate greater than 4000-6000 mesh calcium carbonate greater than 2000-4000 mesh calcium carbonate greater than 1-100nm, and the calcium carbonate is modified by polyethylene glycol;
- the above-mentioned additives are antioxidant, polyethylene wax, anti-mildew masterbatch and essence.
- the added amount of the polyethylene wax is 1.4-1.6%.
- the antioxidant is tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol, and the added amount is 0.01-0.8%.
- the film is prepared from the following raw materials in parts by weight: substrate 50%, surface-modified calcium carbonate filler 45%, its additive 5%;
- the base material is EVA, LDPE and LLDPE with a weight ratio of 1:6:7
- the calcium carbonate includes a particle size range of 2000-4000 mesh, 4000-6000 mesh, Three kinds of calcium carbonate particles of 6000-8000 mesh and 1-100nm, the weight ratio is 6:8:10:1;
- the additives are antioxidant, polyethylene wax, anti-mildew masterbatch and essence.
- a kind of method for preparing above-mentioned thin film is characterized in that, described method comprises the steps:
- the preparation process is simple, the cost is low, and the casting film is suitable for high stretching rate.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
一种薄膜及其制备方法，所述的薄膜由如下重量份原材料制备而成：基材35-48％，表面改性的碳酸钙填料49-51％，其余的为添加剂；所述基材是重量比为1∶(4～9)∶(1～4)的EVA、LDPE和LLDPE，所述碳酸钙包括粒径范围为2000-4000目、4000-6000目、6000-8000目和1-100nm的四种碳酸钙颗粒，所述碳酸钙经聚乙二醇改性处理；所述的添加剂为抗氧剂、聚乙烯蜡、防霉母粒和香精，制备过程简单，成本低，适合高拉伸速率下的流延成膜。
Description
本发明涉及聚烯烃薄膜领域技术，尤其涉及一种碳酸钙高填充量、具有一定力学性能、且适合高拉伸速率下制备的薄膜。
在薄膜制备过程中，碳酸钙填充量偏低，导致成本过高，也有填充比较多的，比如CN102875869，其碳酸钙含量较高，但是PE只能通过拉伸方法流延成膜，且通过低拉伸速率制备的薄膜，其力学性能低于高拉伸速率下的薄膜，且采用两步共混挤出方法，制备过程较为复杂。因此，如何提供一种碳酸钙高填充量、力学性能好且制作过程简单的薄膜很要必要。
为解决上述提到的问题，本发明提供一种如下的技术方案：
一种薄膜，所述的薄膜由如下重量份原材料制备而成：基材 35-48%，表面改性的碳酸钙填料
49-51%，其余的为添加剂；所述的基材是重量比为1:（4~9）：（1~4）的EVA、LDPE和LLDPE，所述的碳酸钙包括有粒径范围为2000-4000目、4000-6000目、6000-8000目和1-100nm的三种碳酸钙颗粒，重量比为（5-10）：（6-11）：（7-12）：（1-2），且四种碳酸钙的含量6000-8000目的碳酸钙大于4000-6000目的碳酸钙大于2000-4000目大于1-100nm的碳酸钙，所述的碳酸钙经聚乙二醇改性处理；所述的添加剂为抗氧剂、聚乙烯蜡、防霉母粒和香精。
作为优选的，所述的聚乙烯蜡的添加量为1.4-1.6%。
作为优选的，所述的抗氧剂为四【β-（3，5-二叔丁基-4-羟基苯基）丙酸】季戊四醇酯，添加量为0.01-0.8%。
作为优选的，所述的薄膜由如下重量份原材料制备而成：基材 50%，表面改性的碳酸钙填料
45%，其添加剂5%；所述的基材是重量比为1:6：7的EVA、LDPE和LLDPE，所述的碳酸钙包括有粒径范围为2000-4000目、4000-6000目、6000-8000目和1-100nm的三种碳酸钙颗粒，重量比为6：8：10：1；所述的添加剂为抗氧剂、聚乙烯蜡、防霉母粒和香精。
一种制备上述的薄膜的方法，其特征在于，所述的方法包括如下的步骤：
1）首先将粒径不同的碳酸钙、基材、抗氧剂、聚乙烯蜡一起加入到密炼机中，加热搅拌充分混合，其后通过双螺杆挤出机挤出、造粒、干燥，挤出温度是180~200℃；
2）按一定重量比例，将防霉母粒、香味母粒及上述步骤1）中得到的母粒，混合加入到流延机中流延成膜，流延机的温度是200~230℃。
制备过程简单，成本低，适合高拉伸速率下的流延成膜。
下面结合具体实施方式对本发明做进一步的解释和说明。
一种薄膜，采用如下的方法制备：
1）首先将粒径不同的碳酸钙、基材、抗氧剂、聚乙烯蜡一起加入到密炼机中，加热搅拌充分混合，其后通过双螺杆挤出机挤出、造粒、干燥，挤出温度是180~200℃；
2）按一定重量比例，将防霉母粒、香味母粒及上述步骤1）中得到的母粒，混合加入到流延机中流延成膜，流延机的温度是200~230℃。
不同的实施例采用不同重量的原材料制备而成，如下表所示：
按上述本发明的步骤，制备出香味高碳酸钙填充防霉聚乙烯薄膜后，其拉伸性能按ASTM D5034-95的标准进行测试。拉伸样品尺寸：长度150毫米，宽度10毫米，拉伸速度为每分钟300毫米，测试结果如下：
表2 所制得流延膜的相关性能
。
Claims (5)
- 一种薄膜，其特征在于，所述的薄膜由如下重量份原材料制备而成：基材 35-48%，表面改性的碳酸钙填料 49-51%，其余的为添加剂；所述的基材是重量比为（0.1-1）:（4~9）：（1~5）的EVA、LLDPE和LDPE，所述的碳酸钙包括有粒径范围为2000-4000目、4000-6000目、6000-8000目和1-100nm的三种碳酸钙颗粒，重量比为（5-10）：（6-11）：（7-12）：（1-2），且四种碳酸钙的含量6000-8000目的碳酸钙大于4000-6000目的碳酸钙大于2000-4000目大于1-100nm的碳酸钙，所述的碳酸钙经聚乙二醇改性处理；所述的添加剂为抗氧剂、聚乙烯蜡、防霉母粒和香精。
- 2.如权利要求1所述的薄膜，其特征在于，所述的聚乙烯蜡的添加量为1.4-1.6%。
- 如权利要求1所述的薄膜，其特征在于，所述的抗氧剂为四【β-（3，5-二叔丁基-4-羟基苯基）丙酸】季戊四醇酯，添加量为0.01-0.8%。
- 如权利要求1所述的薄膜，其特征在于，所述的薄膜由如下重量份原材料制备而成：基材 45%，表面改性的碳酸钙填料 50%，其添加剂5%；所述的基材是重量比为1:6：7的EVA、LDPE和LLDPE，所述的碳酸钙包括有粒径范围为2000-4000目、4000-6000目、6000-8000目和1-100nm的三种碳酸钙颗粒，重量比为6：8：10：1；所述的添加剂为抗氧剂、聚乙烯蜡、防霉母粒和香精。
- 一种制备如权利要求1-4任一权利要求所述的薄膜的方法，其特征在于，所述的方法包括如下的步骤：1）首先将粒径不同的碳酸钙、基材、抗氧剂、聚乙烯蜡一起加入到密炼机中，加热搅拌充分混合，其后通过双螺杆挤出机挤出、造粒、干燥，挤出温度是180~200℃；2）按一定重量比例，将防霉母粒、香味母粒及上述步骤1）中得到的母粒，混合加入到流延机中流延成膜，流延机的温度是200~230℃。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618864A (zh) * | 2004-10-11 | 2005-05-25 | 华东理工大学 | 高填充碳酸钙的硬质聚氯乙烯材料 |
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| CN101040631A (zh) * | 2007-04-20 | 2007-09-26 | 沈阳农业大学 | 金铃大枣保鲜专用膜、袋 |
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| CN102875869A (zh) * | 2012-09-14 | 2013-01-16 | 芮城新泰纳米材料有限公司 | 纳米碳酸钙增强增韧塑料母料及其制备方法 |
| CN106009211A (zh) * | 2016-05-20 | 2016-10-12 | 山西新泰恒信纳米材料有限公司 | 塑编高速拉丝机专用母料及其制备方法 |
| CN106221007A (zh) * | 2016-08-12 | 2016-12-14 | 苏州柯创电子材料有限公司 | 一种改进的高强度耐刮擦聚丙烯材料 |
| CN107793633A (zh) * | 2017-11-30 | 2018-03-13 | 世界家庭用具制品厂有限公司 | 一种具有香味的防霉薄膜及其制备方法 |
-
2021
- 2021-09-30 WO PCT/CN2021/122051 patent/WO2023050259A1/zh unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618864A (zh) * | 2004-10-11 | 2005-05-25 | 华东理工大学 | 高填充碳酸钙的硬质聚氯乙烯材料 |
| CN1821297A (zh) * | 2006-03-09 | 2006-08-23 | 安徽国风集团有限公司 | 一种纳米改性聚乙烯大口径双壁波纹管 |
| CN101040631A (zh) * | 2007-04-20 | 2007-09-26 | 沈阳农业大学 | 金铃大枣保鲜专用膜、袋 |
| CN102372875A (zh) * | 2010-08-24 | 2012-03-14 | 佛山市运通晨塑料助剂有限公司 | 一种超分散高光泽度bopp珠光膜用珠光母料 |
| CN102875869A (zh) * | 2012-09-14 | 2013-01-16 | 芮城新泰纳米材料有限公司 | 纳米碳酸钙增强增韧塑料母料及其制备方法 |
| CN106009211A (zh) * | 2016-05-20 | 2016-10-12 | 山西新泰恒信纳米材料有限公司 | 塑编高速拉丝机专用母料及其制备方法 |
| CN106221007A (zh) * | 2016-08-12 | 2016-12-14 | 苏州柯创电子材料有限公司 | 一种改进的高强度耐刮擦聚丙烯材料 |
| CN107793633A (zh) * | 2017-11-30 | 2018-03-13 | 世界家庭用具制品厂有限公司 | 一种具有香味的防霉薄膜及其制备方法 |
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