CN101597403A - Make the preparation method of the acrylic resin of ultra-high speed biaxially oriented film - Google Patents

Make the preparation method of the acrylic resin of ultra-high speed biaxially oriented film Download PDF

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Publication number
CN101597403A
CN101597403A CNA2008100386285A CN200810038628A CN101597403A CN 101597403 A CN101597403 A CN 101597403A CN A2008100386285 A CNA2008100386285 A CN A2008100386285A CN 200810038628 A CN200810038628 A CN 200810038628A CN 101597403 A CN101597403 A CN 101597403A
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CN
China
Prior art keywords
acrylic resin
oxidant
auxiliary
primary antioxidant
parts
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Pending
Application number
CNA2008100386285A
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Chinese (zh)
Inventor
黄伟东
陈国康
陆秋欢
高国强
王荣和
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Sinopec Shanghai Petrochemical Co Ltd
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Sinopec Shanghai Petrochemical Co Ltd
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Priority to CNA2008100386285A priority Critical patent/CN101597403A/en
Publication of CN101597403A publication Critical patent/CN101597403A/en
Pending legal-status Critical Current

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Abstract

A kind of preparation method who makes the acrylic resin of ultra-high speed biaxially oriented film comprises and will carry out the melting mixing granulation behind acrylic resin base-material and the additive uniform mixing, gets product.The fusion Heating temperature is 180~240 ℃, and fusion heat-up time is 2~4 minutes.The acrylic resin base-material is high isotatic polypropylene, and additive comprises primary antioxidant I and II, and auxiliary anti-oxidant I and II.Wherein: primary antioxidant I is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Primary antioxidant II is 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; Auxiliary anti-oxidant I is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester; Auxiliary anti-oxidant II is two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites.The weight ratio of acrylic resin base-material and additive is 100: 0.10~0.22.

Description

Make the preparation method of the acrylic resin of ultra-high speed biaxially oriented film
Technical field
The present invention relates to a kind of preparation method of acrylic resin, particularly be used to make the preparation method of the acrylic resin of ultra-high speed biaxially oriented film.
Background technology
Biaxially oriented polypropylene film (BOPP) (BOPP) film is one of fastest-rising kind in the polypropylene articles, colourless because of it, do not have smell, tasteless, nontoxic, and have high tensile, high rigidity and a good transparency, so be excellent flexible packing material, also be widely used as the base material of various composite membranes, be the very high coating materials of a kind of added value, development at present is rapid, and uses very extensive.
The bidirectional high speed that a lot of characteristics of BOPP film mainly come from the course of processing stretches, this has the higher requirement except degree of isotacticity, molecular weight and the molecular weight distribution etc. to the acrylic resin base-material, also requires to overcome the polymer macromolecule that causes because of oxidation in the drawing process and decomposes.Because the processing of film is carried out under the aerobic state of high temperature, long flow process, thermooxidative degradation can take place in polymer macromolecule, thereby has a strong impact on the ductility of polymkeric substance, and rupture of membranes very easily takes place during stretching.Therefore make in the raw material acrylic resin of BOPP film and must contain oxidation resistant additive, certainly, additive also has the effect that improves film oxidation resistent susceptibility in the life-time service process simultaneously.At present, the processing technology of BOPP film develops to the direction of high linear speed, big fabric width, high yield, and linear speed develops into 400~500m/min by 200m/min, is referred to as the ultra-high speed two-way stretch.Meanwhile, film thickness also reduced to 10~18 μ m by 15~38 former μ m.Everything is all had higher requirement to the raw material acrylic resin of making the BOPP film, will guarantee that not only it possesses good film forming processing characteristics, also will make the film that makes have favorable mechanical performance and optical property.At this wherein, the quality of additive performance plays a part very crucial.Generally speaking, the appropriateness increase that relies on the additive add-on also can obtain better oxidation-resistance, but this will cause the quality of film to descend, even makes the film forming poor processability on the contrary.Still there is the defective of this respect in what for existing acrylic resin that is used to make the ultra-high speed biaxially oriented film or its preparation method, so the research of additive performance receives much concern always.
Summary of the invention
The invention provides a kind of preparation method who makes the acrylic resin of ultra-high speed biaxially oriented film, it improves the additive that adopts, technical problem to be solved is to make the acrylic resin of preparation gained can not only satisfy the processing requirement of ultra-high speed two-way stretch film forming processing, and can guarantee to have more good mechanical property and optical property as the BOPP film of raw material manufacturing.
Below be the concrete technical scheme of the present invention:
A kind of preparation method who is used to make the acrylic resin of ultra-high speed biaxially oriented film, this method comprises and will carry out the melting mixing granulation behind acrylic resin base-material and the additive uniform mixing, obtain the acrylic resin product, the fusion Heating temperature is 180~240 ℃, and fusion heat-up time is 2~4 minutes.
Above-mentioned acrylic resin base-material is high isotatic polypropylene, and its melt flow rate (MFR) is 2.50~3.50g/10min, and degree of isotacticity is 95.0~98.0%;
Above-mentioned additive comprises primary antioxidant I and II, and auxiliary anti-oxidant I and II, wherein:
Primary antioxidant I is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester,
Primary antioxidant II is 1,3,5-trimethylammonium-2,4, and 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene,
Auxiliary anti-oxidant I is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester,
Auxiliary anti-oxidant II is two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
The components of additives proportioning is in weight part, and when primary antioxidant I was 100 parts, primary antioxidant II was 20~35 parts, and auxiliary anti-oxidant I is 32~45 parts, and auxiliary anti-oxidant II is 16~27 parts.
The weight ratio of acrylic resin base-material and additive is 100: 0.10~0.22.
Above-mentioned fusion Heating temperature is preferably 190~220 ℃.
Above-mentioned components of additives proportioning is in weight part, and when primary antioxidant I was 100 parts, primary antioxidant II was preferably 25~35 parts; Auxiliary anti-oxidant I is preferably 35~40 parts; Auxiliary anti-oxidant II is preferably 16~22 parts.
The weight ratio of above-mentioned acrylic resin base-material and additive is preferably 100: 0.12~and 0.18.
Key of the present invention is that additive is improved, and the contriver found through experiments, and selected these oxidation inhibitor are with suitable ratio compatibility, and its antioxidant effect plays a part collaborative, and performance greatly improves, thereby the interpolation total amount of additive is minimized.Strict additive also belongs to a kind of impurity in the polypropylene base-material in fact, and under the prerequisite that guarantees antioxygen property, the minimizing of adding total amount is obviously very favourable to the reduction of the raising of the raising of film forming processibility, film article intensity and turbidity.Therefore, compared with prior art, method provided by the invention has guaranteed that not only the resin that makes has good processing properties, satisfies the complete processing requirement of ultra-high speed two-way stretch, and makes as the BOPP film of raw material manufacturing and have more good mechanical property and optical property.
The invention will be further described below by embodiment.Because key of the present invention is the improvement of additive, other parts such as melting mixing granulation process and prior art are basic identical, so embodiment will pay attention to enumerating of additive formulations and addition testing data.
Embodiment
[embodiment 1~8]
Get powdered polypropylene resin binder 500kg,, mix thoroughly in each component of required ratio adding additive.Material drops into twin screw extruder and carries out the melting mixing granulation.The residence time of material in screw rod is 2~4 minutes, and extruder temperature is controlled to be 190~220 ℃.The acrylic resin particle that obtains is finished product behind cooling drying, each embodiment makes the 500kg sample.
The acrylic resin base-material is high isotatic polypropylene, and its melt flow rate (MFR) is 2.50~3.50g/10min, and degree of isotacticity is 95.0~98.0%.
Additive is by primary antioxidant I and II, and auxiliary anti-oxidant I and II composition, wherein:
Primary antioxidant I is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester,
Primary antioxidant II is 1,3,5-trimethylammonium-2,4, and 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene,
Auxiliary anti-oxidant I is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester,
Auxiliary anti-oxidant II is two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
The add-on of each embodiment components of additives proportioning and additive sees Table 1, and wherein the components of additives proportioning is the weight part of other component when primary antioxidant I is 100 weight parts; The add-on of additive is the weight part of additive when the acrylic resin base-material is 100 weight parts.
The acrylic resin finished product that each embodiment obtains adopts ultra-high speed BOPP processes film, and the processing linear speed is 475m/min, and film thickness is 18 μ m.The main performance index of testing film the results are shown in Table 2 after timeliness.
Table 1.
Primary antioxidant II Auxiliary anti-oxidant I Auxiliary anti-oxidant II The additive add-on
Embodiment 1 20 32 27 0.10
Embodiment 2 25 32 22 0.12
Embodiment 3 28 35 20 0.15
Embodiment 4 30 35 18 0.15
Embodiment 5 30 40 20 0.20
Embodiment 6 32 40 16 0.16
Embodiment 7 35 45 18 0.18
Embodiment 8 35 45 16 0.22
Table 2.
Tensile strength (MPa) Modulus in tension (N/mm 2) Mist degree (%)
Embodiment 1 162 1890 1.68
Embodiment 2 167 1915 1.66
Embodiment 3 170 1930 1.78
Embodiment 4 172 1962 1.80
Embodiment 5 174 1992 1.82
Embodiment 6 170 1975 1.82
Embodiment 7 169 1963 1.86
Embodiment 8 167 1942 1.89

Claims (6)

1, a kind of preparation method who makes the acrylic resin of ultra-high speed biaxially oriented film, this method comprises and will carry out the melting mixing granulation behind acrylic resin base-material and the additive uniform mixing, obtain the acrylic resin product, the fusion Heating temperature is 180~240 ℃, fusion heat-up time is 2~4 minutes
Above-mentioned acrylic resin base-material is high isotatic polypropylene, and its melt flow rate (MFR) is 2.50~3.50g/10min, and degree of isotacticity is 95.0~98.0%;
Above-mentioned additive comprises primary antioxidant I and II, and auxiliary anti-oxidant I and II, wherein:
Primary antioxidant I is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester,
Primary antioxidant II is 1,3,5-trimethylammonium-2,4, and 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene,
Auxiliary anti-oxidant I is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester,
Auxiliary anti-oxidant II is two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites,
The components of additives proportioning is in weight part, and when primary antioxidant I was 100 parts, primary antioxidant II was 20~35 parts, and auxiliary anti-oxidant I is 32~45 parts, and auxiliary anti-oxidant II is 16~27 parts;
The weight ratio of acrylic resin base-material and additive is 100: 0.10~0.22.
2, the preparation method of acrylic resin according to claim 1 is characterized in that described fusion Heating temperature is 190~220 ℃.
3, the preparation method of acrylic resin according to claim 1 is characterized in that described components of additives proportioning in weight part, and when primary antioxidant I was 100 parts, primary antioxidant II was 25~35 parts.
4, the preparation method of acrylic resin according to claim 1 is characterized in that described components of additives proportioning in weight part, and when primary antioxidant I was 100 parts, auxiliary anti-oxidant I was 35~40 parts.
5, the preparation method of acrylic resin according to claim 1 is characterized in that described components of additives proportioning in weight part, and when primary antioxidant I was 100 parts, auxiliary anti-oxidant II was 16~22 parts.
6, the preparation method of acrylic resin according to claim 1, the weight ratio that it is characterized in that described acrylic resin base-material and additive is 100: 0.12~0.18.
CNA2008100386285A 2008-06-05 2008-06-05 Make the preparation method of the acrylic resin of ultra-high speed biaxially oriented film Pending CN101597403A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014048546A1 (en) * 2012-09-28 2014-04-03 Clariant International Ltd Process for preparing a polypropylene-based object having an increased surface energy
CN111454517A (en) * 2020-05-13 2020-07-28 东华能源(宁波)新材料有限公司 Polypropylene resin special for high-speed biaxially oriented film and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014048546A1 (en) * 2012-09-28 2014-04-03 Clariant International Ltd Process for preparing a polypropylene-based object having an increased surface energy
CN104812814A (en) * 2012-09-28 2015-07-29 科莱恩金融(Bvi)有限公司 Process for preparing a polypropylene-based object having an increased surface energy
CN104812814B (en) * 2012-09-28 2018-10-23 科莱恩金融(Bvi)有限公司 It is used to prepare the method based on polyacrylic article with increased surface energy
CN111454517A (en) * 2020-05-13 2020-07-28 东华能源(宁波)新材料有限公司 Polypropylene resin special for high-speed biaxially oriented film and preparation method and application thereof

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