CN113493584A - Method for regulating and controlling content of isotactic poly-1-butene crystal form III through cooling rate - Google Patents
Method for regulating and controlling content of isotactic poly-1-butene crystal form III through cooling rate Download PDFInfo
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- CN113493584A CN113493584A CN202010193037.6A CN202010193037A CN113493584A CN 113493584 A CN113493584 A CN 113493584A CN 202010193037 A CN202010193037 A CN 202010193037A CN 113493584 A CN113493584 A CN 113493584A
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Abstract
The invention discloses a method for regulating and controlling the content of an isotactic poly-1-butylene crystal form III through a cooling rate, which comprises the steps of blending 100 parts of isotactic polybutene-1 powder, 0.2-1 part of antioxidant and 1-3 parts of additive, uniformly dispersing, heating, melting, extruding and granulating to obtain the isotactic polybutene-1 containing a crystal form III structure, heating to 150-200 ℃, and cooling to 30 ℃ at a cooling rate of 2-30 ℃/min after constant temperature. In the invention, the content of the crystal form III obtained at different cooling rates is different, which shows that the cooling rate has great influence on the content of the crystal form III, and a feasible way is provided for directly obtaining the crystal form III from the isotactic poly-1-butene body.
Description
Technical Field
The invention belongs to the technical field of polymer crystal form regulation and control, and particularly relates to a method for regulating and controlling the content of an isotactic poly-1-butene crystal form III through a cooling rate.
Background
Isotactic poly-1-butene (iPB-1) is a polymer obtained by polymerizing 1-butene as a raw material with or without addition of a comonomer under a specific catalyst system. Poly-1-butene is one of typical polymorphic polymer representatives and has five crystal structures of I, I ', II' and III. Form III shows an orthogonal unit cell structure built up from 4/1 helices. The prior art shows that the crystal form III can be directly obtained by the methods of solution crystallization, substrate epitaxial growth and the like, and the melting point of the crystal form III is about 98 ℃. The literature on the crystal form III mostly focuses on the regulation of growth, but few reports in the literature show that the crystal form III with different contents can be obtained by crystallization from an isotactic poly-1-butene body through regulating and controlling the cooling rate. It would therefore be of great interest if a method could be developed for controlling the content of isotactic poly-1-butene crystalline form III by means of a cooling rate.
Disclosure of Invention
The invention aims to make up the defects of the existing preparation technology of the crystal form III, and provides a method for regulating and controlling the content of the crystal form III of isotactic poly-1-butene by cooling rate.
The technical purpose of the invention is realized by the following technical scheme.
A method for regulating and controlling the content of an isotactic poly-1-butene crystal form III through a cooling rate comprises the following steps:
step 1, blending isotactic polybutene-1, an antioxidant and an additive to disperse uniformly, heating and melting, extruding and granulating to obtain isotactic polybutene-1 granules containing a crystal form III structure, wherein: the dosage of the isotactic polybutene-1 is 100 parts by mass, the dosage of the antioxidant is 0.3-0.5 part by mass, and the dosage of the dendritic hyperbranched polyester as the additive is 1-3 parts by mass;
in step 1, the number average molecular weight of isotactic polybutene-1 is 27.4X 105g/mol, molecular weight distribution 5.5.
In the step 1, the antioxidant is prepared from antioxidant 168 and antioxidant 1098 according to the mass ratio of 2: 1 addition.
In step 1, the dendritic hyperbranched polyester as the additive is aliphatic hyperbranched polyester hyper H104.
And 2, carrying out DSC test on the isotactic polybutene-1 granules containing the crystal form III structure obtained in the step 1, heating to a temperature above the equilibrium melting point, melting, preserving heat, cooling to room temperature at different cooling rates, and carrying out heating and cooling circulation twice, wherein the first heating and cooling is used for eliminating heat history, and the content of the isotactic polybutene-1 crystal form III can be regulated and controlled at different cooling rates in the second heating and cooling.
In the step 2, the temperature is raised to 150-200 ℃ from the room temperature of 20-25 ℃ at the speed of 10-30 ℃/min, the temperature is kept for 3-5 min, then the temperature is lowered to the room temperature of 20-25 ℃ at the speed of 1-30 ℃/min, and the temperature is raised again under the same condition, so that the melting peak of the crystal form III can be observed.
The technical method provided by the invention is suitable for isotactic polybutene-1, and after a proper additive is added, the isotactic polybutene-1 is extruded and granulated, and the crystal form III can be obtained by directly crystallizing from a body. By changing different cooling rates, the crystal form III with different contents can be obtained. The additive used in the invention can promote the generation of the crystal form III, and the crystal form III with different contents can be obtained by changing the cooling rate. The patent provides an effective way for regulating and controlling the content of the isotactic poly-1-butylene crystal form III through the cooling rate.
Drawings
FIG. 1 is a DSC melting curve diagram of crystal form III and crystal form II obtained at a cooling rate of 30 deg.C/min in the present invention.
FIG. 2 is a DSC melting curve diagram of crystal form III and crystal form II obtained at a cooling rate of 20 deg.C/min in the present invention.
FIG. 3 is a DSC melting curve diagram of crystal form III and crystal form II obtained at a cooling rate of 10 deg.C/min in the present invention.
FIG. 4 is a DSC melting curve diagram of crystal form III and crystal form II obtained at a cooling rate of 5 deg.C/min in the present invention.
FIG. 5 is a DSC melting curve diagram of crystal form III and crystal form II obtained at a cooling rate of 2 deg.C/min in the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
100 portions of isotactic polybutene-1 powder (Shandong Oriental Macro chemical Co., Ltd., number average molecular weight 27.4X 10)5g/mol, molecular weight distribution of 5.5, each part is 1g), 0.5 part of antioxidant (antioxidant 168 and antioxidant 1098 according to the mass ratio of 2: 1, 1g of new Tianjin Lianlong material company, 1g of each part, 3 parts of dendritic hyperbranched polyester (Wuhan hyperbranched resin technology company, hyper H104 aliphatic hyperbranched polyester, 1g of each part) as an additive, blending, and extruding and granulating by using a double-screw extruder (SHJ-20B, Nanjing Jie Ente) to obtain isotactic polybutene-1, wherein the temperature of the extruder is set as follows, one area: 140 ℃; and a second zone: 170 ℃; and (3) three zones: 180 ℃; and (4) four areas: 180 ℃; and a fifth zone: 180 ℃; a sixth zone: 180 ℃; seven areas: 180 ℃; and eight regions: 180 ℃ is carried out.
A7 mg sample was weighed, placed in an aluminum crucible, placed in DSC (LNP95, Linkam) equipment, heated to 150 ℃ at 10 ℃/min and maintained at the constant temperature for 5min, then cooled to 30 ℃ at 30 ℃/min, heated to 150 ℃ again at 10 ℃/min and maintained at the constant temperature for 5min, and the obtained melting curve is shown in FIG. 1. Then heating to 150 deg.C at 10 deg.C/min and holding the temperature for 5min, then cooling to 30 deg.C at 20 deg.C/min, heating to 150 deg.C at 10 deg.C/min and holding the temperature for 5min to obtain a melting curve as shown in FIG. 2. Cooling to 30 deg.C at cooling rate of 10 deg.C min, 5 deg.C/min, and 2 deg.C/min, respectively, and heating again to obtain corresponding melting curve, as shown in FIG. 3, FIG. 4, and FIG. 5. As shown in fig. 1 to 5, the temperature rise and fall are performed twice, the first temperature rise and fall is to eliminate the thermal history, the second temperature rise can observe the melting peak of the crystal form III at about 99 ℃, and the melting peak at 99 ℃ is the melting peak of the crystal form III, which indicates that the crystal form III is generated, and the areas of the melting peaks are different at different cooling rates. According to the content recorded in the invention, after an antioxidant and an additive are added into the isotactic polybutene-1 powder, the isotactic polybutene-1 material containing a crystal form III structure can be obtained by extrusion granulation. DSC tests prove that the content of the crystal form III can be regulated and controlled by regulating different cooling rates.
It should be noted that the subject group has been engaged in research on polybutene-1 materials, and the research and development of polybutene-1 materials for generating crystal form III was carried out before, and the chinese invention application "a method for generating crystal form III by crystallization from isotactic polybutene-1 bodies" (application No. 202010184453X, application date 3/16/2020) was filed before the present application, and the above chinese invention application is incorporated in the present application in its entirety, and research is continued on the basis of the above invention application to find the relationship between the "cooling rate and the content of crystal form III", so that the present application is proposed as continuation and supplement of the above invention application.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (5)
1. A method for regulating and controlling the content of an isotactic poly-1-butene crystal form III through a cooling rate is characterized by comprising the following steps:
step 1, blending isotactic polybutene-1, an antioxidant and an additive to disperse uniformly, heating and melting, extruding and granulating to obtain isotactic polybutene-1 granules containing a crystal form III structure, wherein: the dosage of the isotactic polybutene-1 is 100 parts by mass, the dosage of the antioxidant is 0.3-0.5 part by mass, and the dosage of the dendritic hyperbranched polyester as the additive is 1-3 parts by mass;
and 2, carrying out DSC test on the isotactic polybutene-1 granules containing the crystal form III structure obtained in the step 1, heating to a temperature above the equilibrium melting point, melting, preserving heat, cooling to room temperature at different cooling rates, and carrying out heating and cooling circulation twice, wherein the first heating and cooling is used for eliminating heat history, and the content of the isotactic polybutene-1 crystal form III can be regulated and controlled at different cooling rates in the second heating and cooling.
2. The method for regulating and controlling the content of the isotactic polybutene-1 crystal form III by cooling rate as claimed in claim 1, wherein in step 1, the isotactic polybutene-1 has a number average molecular weight of 27.4X 105g/mol, molecular weight distribution 5.5.
3. The method for regulating and controlling the content of the isotactic poly-1-butene crystal form III through the cooling rate according to claim 1, wherein in the step 1, the antioxidant is prepared from antioxidant 168 and antioxidant 1098 in a mass ratio of 2: 1 addition.
4. The method for regulating and controlling the content of the isotactic poly-1-butene crystal form III through the cooling rate according to claim 1, wherein in the step 1, the dendritic hyperbranched polyester as the additive is aliphatic hyperbranched polyester hyper H104.
5. The method for regulating and controlling the content of the isotactic poly-1-butene crystal form III through the cooling rate according to claim 1, wherein in the step 2, the temperature is raised from room temperature of 20-25 ℃ to 150-200 ℃ at a speed of 10-30 ℃/min, the temperature is kept for 3-5 min, then the temperature is lowered to room temperature of 20-25 ℃ at a speed of 1-30 ℃/min, and the temperature is raised again under the same condition, so that the melting peak of the crystal form III at about 99 ℃ can be observed.
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| US4110524A (en) * | 1968-02-27 | 1978-08-29 | Chemische Werks Huels A.G. | Direct production of polymorph iii of isotactic polybutene-1 |
| WO2008064958A1 (en) * | 2006-12-01 | 2008-06-05 | Basell Poliolefine Italia S.R.L. | Process for preparing polybutene compositions having increased crystallization temperature |
| CN103819596A (en) * | 2012-11-16 | 2014-05-28 | 中国石油天然气股份有限公司 | Preparation method of isotactic poly-1-butene |
| CN107254055A (en) * | 2017-06-20 | 2017-10-17 | 天津大学 | A kind of brilliant crystallization generation I method directly from isotactic poly- 1 butylene body |
| CN107531966A (en) * | 2015-04-22 | 2018-01-02 | 三井化学株式会社 | Poly- 1 butylene resin composition and formed body therefrom |
| CN110684282A (en) * | 2019-10-30 | 2020-01-14 | 南京聚隆科技股份有限公司 | 3D hollow blow molding micro-foaming polyolefin material and preparation method thereof |
| CN110791028A (en) * | 2019-11-11 | 2020-02-14 | 太原科技大学 | Preparation method and application of special aid for efficiently inducing crystal form transformation of polybutene-1 |
| CN113402818A (en) * | 2020-03-16 | 2021-09-17 | 天津大学 | Method for generating crystal form III through crystallization from isotactic poly-1-butene body |
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2020
- 2020-03-18 CN CN202010193037.6A patent/CN113493584A/en active Pending
Patent Citations (8)
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| US4110524A (en) * | 1968-02-27 | 1978-08-29 | Chemische Werks Huels A.G. | Direct production of polymorph iii of isotactic polybutene-1 |
| WO2008064958A1 (en) * | 2006-12-01 | 2008-06-05 | Basell Poliolefine Italia S.R.L. | Process for preparing polybutene compositions having increased crystallization temperature |
| CN103819596A (en) * | 2012-11-16 | 2014-05-28 | 中国石油天然气股份有限公司 | Preparation method of isotactic poly-1-butene |
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Application publication date: 20211012 |