CN101157771B - Supported beta crystal core formation agent and preparation method thereof - Google Patents
Supported beta crystal core formation agent and preparation method thereof Download PDFInfo
- Publication number
- CN101157771B CN101157771B CN2007100306483A CN200710030648A CN101157771B CN 101157771 B CN101157771 B CN 101157771B CN 2007100306483 A CN2007100306483 A CN 2007100306483A CN 200710030648 A CN200710030648 A CN 200710030648A CN 101157771 B CN101157771 B CN 101157771B
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- nano
- calcium carbonate
- dicarboxylic acid
- beta
- present
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- 239000013078 crystal Substances 0.000 title claims description 29
- 230000015572 biosynthetic process Effects 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 29
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 15
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 abstract description 4
- 239000008116 calcium stearate Substances 0.000 abstract description 4
- 235000013539 calcium stearate Nutrition 0.000 abstract description 4
- 239000002667 nucleating agent Substances 0.000 abstract 4
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 description 19
- -1 polypropylene Polymers 0.000 description 18
- 229920001155 polypropylene Polymers 0.000 description 18
- 238000010899 nucleation Methods 0.000 description 9
- 230000006911 nucleation Effects 0.000 description 9
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- TXZLDPUFIHXKPH-UHFFFAOYSA-N lanthanum;octadecanoic acid Chemical compound [La].CCCCCCCCCCCCCCCCCC(O)=O TXZLDPUFIHXKPH-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention discloses a load-type Beta-nucleating agent and a preparation method thereof, the load-type Beta-nucleating agent of the present invention consists of nano calcium carbonate and aliphatic dicarboxylic acid, and the weight ratio of which is 5 to 1000: 1. The present invention adopts the nano calcium carbonate with a big surface area as a carrier, adopts a simple method to highly disperse the dicarboxylic acid on the nano-calcium carbonate surface, makes use of a chemical reaction of the nano-calcium carbonate and the dicarboxylic acid to form the high efficient beta-nucleating agent which is the same with the mixture of pimelic acid and calcium stearate aiming at the problems of the existing beta-nucleating agents. The present invention realizes the purposes of reducing the consumption of the dicarboxylic acid, reducing the cost and improving the nucleating efficiency as the dicarboxylic acid on the nano-calcium carbonate is highly dispersed and the effective nucleating points are only formed on the surface of the nano-calcium carbonate.
Description
Technical field
The present invention relates to brilliant nucleator of β and technology of preparing thereof.
Background technology
Beta-crystal polypropylene is new variety in the polypropylene, it is except that having kept α crystal polypropylene good comprehensive performances, compare with the α crystal polypropylene, also has the shock strength that is several times as much as the α crystal polypropylene, heat-drawn wire increases substantially, low tensile yield strength and modulus in tension show high toughness and ductility under high-speed stretch, have characteristics such as tangible strain hardening.To have a wide range of applications with aspects such as microporous membrane and microporous fibres in industrial pipeline, battery cell case, film, gaseous interchange.At present, adding the brilliant nucleator of β is the most effectual way that obtains the high-content beta-crystal polypropylene.So far, the brilliant nucleator of β mainly contains: (1) organic dye.The condensed ring organism that has the directrix plane structure as quinacridone red (E3B) etc.; Some salt of (2) II a family metallic elements and the mixture of di-carboxylic acid.As pimelic acid and calcium stearate mixture class; (3) substituted amide class.As N, N '-dicyclohexyl amine base terephthaloyl amine etc.; (4) rare earth nucleator etc.The rare earth compounding nucleator that is mixed with as stearic acid lanthanum and stearic acid.Yet what the brilliant nucleator of above β had exists nucleation efficient low, the cost height, and thermotolerance is low, and is poor with the PP consistency, easily makes problems such as color articles.
Summary of the invention
The supported beta crystal core formation agent that the purpose of this invention is to provide a kind of nucleation efficient height, cost is low and has enhancement.
Another object of the present invention provides the preparation method of the simple supported beta crystal core formation agent of a kind of step.
Supported beta crystal core formation agent of the present invention is made up of nano-calcium carbonate and aliphatic dicarboxylic acid, and its weight ratio is 5-1000: 1.Preferred pimelic acid of described aliphatic dicarboxylic acid or suberic acid.
Problem at the brilliant nucleator existence of existing β, the present invention adopts the method for the big nano-calcium carbonate of surface-area as carrier, adopt simple method that di-carboxylic acid is disperseed at the nano-calcium carbonate surface elevation, utilize the nano-calcium carbonate and the chemical action of di-carboxylic acid to form brilliant nucleator as the pimelic acid β efficiently identical with calcium stearate mixture class.Because di-carboxylic acid is in the nano-calcium carbonate high dispersing, and only form effective nucleation site, thereby realize reducing the di-carboxylic acid consumption, reduce cost, improve the purpose of nucleation efficient on the nano-calcium carbonate surface.
The preparation method of supported beta crystal core formation agent of the present invention:
Method 1: after aliphatic dicarboxylic acid usefulness solvent (for example acetone) dissolving, with the nano-calcium carbonate mixed at room temperature, room temperature or low temperature solvent flashing promptly obtain supported beta crystal core formation agent.
Method 2: aliphatic dicarboxylic acid is directly mixed with the nano-calcium carbonate room temperature, promptly obtain supported beta crystal core formation agent.
Utilize of the effect of high surface area nano-calcium carbonate as carrier, di-carboxylic acid is disperseed at the nano-calcium carbonate surface elevation, utilize the nano-calcium carbonate and the chemical action of di-carboxylic acid to form brilliant nucleator as the pimelic acid β efficiently identical with calcium stearate mixture class.Because di-carboxylic acid is in the nano-calcium carbonate high dispersing, and only form effective nucleation site, thereby realize reducing the di-carboxylic acid consumption, reduce cost, improve the purpose of nucleation efficient on the nano-calcium carbonate surface.
Supported beta crystal core formation agent of the present invention is compared with the brilliant nucleator of existing non-loading type β, has following beneficial effect:
(1) nano-calcium carbonate makes the aliphatic dicarboxylic acid high dispersing on the nano-calcium carbonate surface as carrier, and the effective nucleation site that causes forming increases, and nucleation efficient improves.
(2) nano-calcium carbonate reduces the aliphatic dicarboxylic acid consumption as carrier, realizes the reduction of nucleator cost.
(3) nano-calcium carbonate is as carrier, polypropylene is also played the enhancing toughening effect, the yield strength and the modulus of beta-crystal polypropylene are improved, solve the brilliant nucleator nucleation of non-loading type β polypropylene and have yield strength and the low problem of modulus, help the expansion of beta-crystal polypropylene purposes.
(4) nano-calcium carbonate is as carrier, and beta-crystal polypropylene more helps producing porous membrane.
Description of drawings
Fig. 1 is embodiment 5 crystallization WAXD curve under differing temps;
Fig. 2 is that embodiment 5 is at the WAXD of different rates decrease temperature crystalline curve.
Embodiment
Aliphatic dicarboxylic acid is dissolved in acetone, and with the nano-calcium carbonate mixed at room temperature, 15 ℃ of acetone solvents that volatilize down promptly obtain supported beta crystal core formation agent.Again the brilliant nucleator of β is added to preparation high-content beta-crystal polypropylene in the polypropylene.
The composition proportion of the supported beta crystal core formation agent of various embodiments of the present invention and polypropylene beta crystal content are as shown in table 1.
Table 1. is added with the polyacrylic beta crystal content of supported beta crystal core formation agent
The WAXD curve of the embodiment of the invention is seen Fig. 1 and 2.The WAXD curve of Fig. 1 and 2 shows that the polypropylene that adds supported beta crystal core formation agent only has the diffraction peak of beta-crystal polypropylene, does not have the diffraction peak of α crystal polypropylene substantially, and the beta-crystal polypropylene content that calculates according to diffraction peak sees Table 1.
Claims (1)
1. a supported beta crystal core formation agent is characterized in that being made up of nano-calcium carbonate and aliphatic dicarboxylic acid, and its weight ratio is 5-1000: 1; Described aliphatic dicarboxylic acid is pimelic acid or suberic acid; With aliphatic dicarboxylic acid with acetone solution after, with the nano-calcium carbonate mixed at room temperature, solvent flashing when room temperature or 15 ℃ promptly obtains supported beta crystal core formation agent.
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| CN2007100306483A CN101157771B (en) | 2007-09-29 | 2007-09-29 | Supported beta crystal core formation agent and preparation method thereof |
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| CN2007100306483A CN101157771B (en) | 2007-09-29 | 2007-09-29 | Supported beta crystal core formation agent and preparation method thereof |
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| Publication Number | Publication Date |
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| CN101157771A CN101157771A (en) | 2008-04-09 |
| CN101157771B true CN101157771B (en) | 2010-09-08 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941296A (en) * | 2010-09-01 | 2011-01-12 | 宿迁市景宏彩印包装有限公司 | Method for preparing high-power lithium ion battery diaphragm |
| CN101955610A (en) * | 2010-10-12 | 2011-01-26 | 中山大学 | Calcium carbonate fillers having high beta-nucleation effect on polypropylene and copolymers of polypropylene and preparation method thereof |
| CN102086285A (en) * | 2010-12-09 | 2011-06-08 | 中山大学 | Eggshell filler having high beta nucleation on polypropylene and preparation method thereof |
| CN102558683B (en) * | 2011-12-31 | 2014-01-22 | 广州呈和科技有限公司 | Polypropylene beta crystal form nucleating agent composition and application thereof |
| CN111363201B (en) * | 2020-05-09 | 2021-03-23 | 吉林大学 | Composite material and preparation method thereof, nucleating agent and application |
| CN115710381A (en) * | 2022-11-01 | 2023-02-24 | 呈和科技股份有限公司 | Polypropylene composite additive and application thereof |
| CN117024878A (en) * | 2023-08-24 | 2023-11-10 | 山东路德新材料股份有限公司 | Modified polypropylene geogrid raw material and geogrid |
| CN116769253B (en) * | 2023-08-24 | 2023-12-12 | 山东路德新材料股份有限公司 | Geogrid modified polypropylene engineering plastic and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108716A (en) * | 1985-11-22 | 1988-01-20 | 兰州化学工业公司化工研究院 | The preparation of Beta-crystalline polyacrylic resin material and the composition of goods thereof |
| WO2002081557A1 (en) * | 2001-04-04 | 2002-10-17 | 3M Innovative Properties Company | Microporous materials and methods of making the same |
| CN1580124A (en) * | 2003-08-01 | 2005-02-16 | 上海普利特复合材料有限公司 | Inorganic nano microparticle nucleation glass fiber reinforced polyester composite material |
-
2007
- 2007-09-29 CN CN2007100306483A patent/CN101157771B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108716A (en) * | 1985-11-22 | 1988-01-20 | 兰州化学工业公司化工研究院 | The preparation of Beta-crystalline polyacrylic resin material and the composition of goods thereof |
| WO2002081557A1 (en) * | 2001-04-04 | 2002-10-17 | 3M Innovative Properties Company | Microporous materials and methods of making the same |
| CN1580124A (en) * | 2003-08-01 | 2005-02-16 | 上海普利特复合材料有限公司 | Inorganic nano microparticle nucleation glass fiber reinforced polyester composite material |
Non-Patent Citations (1)
| Title |
|---|
| 罗本喆.纳米碳酸钙/庚二酸复合成核剂对热致相分离法制备聚丙烯微孔膜的影响.高分子学报 第7期.2006,(第7期),866-872. * |
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| CN101157771A (en) | 2008-04-09 |
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Application publication date: 20080409 Assignee: Shenzhen Fengzhao Technology Co., Ltd. Assignor: Sun Yat-sen University Contract record no.: 2014440020102 Denomination of invention: Supported beta crystal core formation agent and preparation method thereof Granted publication date: 20100908 License type: Exclusive License Record date: 20140403 |
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