CN105622627A - DBS polyolefin nucleating agent and preparation method and application thereof - Google Patents
DBS polyolefin nucleating agent and preparation method and application thereof Download PDFInfo
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- CN105622627A CN105622627A CN201610076421.1A CN201610076421A CN105622627A CN 105622627 A CN105622627 A CN 105622627A CN 201610076421 A CN201610076421 A CN 201610076421A CN 105622627 A CN105622627 A CN 105622627A
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- sorbitol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1575—Six-membered rings
Abstract
The invention relates to a DBS polyolefin nucleating agent and a preparation method and application thereof. The DBS polyolefin nucleating agent is one of 1,3:2,4-di(3-fluoro-4- tertiary butyl benzyl) sorbitol, 1,3:2,4-di(3,5-difluoro-4-tertiary butyl-benzyl) sorbitol, 1,3:2,4-di(3,5-difluoro-4-ethyl-benzyl) sorbitol, 1,3:2,4-di(3-fluoro-4-ethyl-benzyl) sorbitol, 1,3:2,4-di(3-fluoro-4-isopropyl-benzyl) sorbitol, and the like. The nucleating agent can be used for effectively accelerating crystallization of polyolefin resin, heightening degree of crystallinity of the polyolefin resin and enabling polyolefin to be improved in transparency and surface brightness, flexural modulus, tensile yield strength, distortion temperature, impact strength and the like of the polyolefin are heightened, and the problem that transparent plastics have pungent smell during traditional processing of sorbitol nucleating agents can be solved obviously, so that the DBS polyolefin nucleating agent can be used for processing of food and medical packaging materials.
Description
Technical field
The present invention relates to a kind of DBS class polyolefin nucleating agent and its preparation method and application.
Background technology
In recent years, the yield along with vistanex increases rapidly, and its processed and applied field is more and more extensive. People's requirement also increasingly stringent while living standard improves constantly, to plastic. Nucleator is as polyolefinic a kind of excellent modified additive, addition just can be greatly reduced the mist degree of plastic a little, enhance the transparency and heat distortion temperature, product strength detail improves, and largely improves its application performance, final its Additional Value of Commodities of raising. Its development and application causes the common concern of countries in the world.
Polyolefin nucleating agent chemically structure can be divided into mineral-type, organic and high score subclass three kinds, and wherein organic nucleator has best nucleation modified effect and serviceability, is the most active and most popular class in nucleator research. Organic nucleator refers to the organic compound with relatively low relative molecular mass, and it mainly includes the nucleator such as dibenzal sorbitol and derivatives class, carboxylic acid and metallic salt, organic phosphoric acid metallic salt, amide-type.
The developmental research of dibenzal sorbitol and homologous derivatives thereof nucleator thereof, is the hot fields of recent domestic research. Since a first section in 1972 has the Japan Patent appearance of industrialization meaning, the synthetic technology of such nucleator has had bigger development.
20 century 70s, Japanese Hamad finds, adds dibenzal sorbitol (DBS) and can improve the transparency and the glossiness of PP, improve the heat distortion temperature of PP, rigidity so that the crystallization rate of PP is accelerated, processing and forming cycle time in PP. From then on, this PP modification technology worldwide obtains commonly used, and starts realization the eighties in 20th century and commercially produce.
Milliken chemical company of the U.S. has in succession succeeded in developing Millad3905, Millad3940, Millad3988 homologous derivatives thereof nucleator and has put on market, and achieves and apply effect preferably. Lanzhou Petrochemical Company Petroleum Chemical Engineering Institute develops DBS and the launch products of 5 trades mark of homologous derivatives thereof thereof in succession, all achieves and applies effect preferably.
But it is bigger that current polyolefin nucleating agent on the market has abnormal smells from the patient, improve the shortcomings such as the transparency is not high with nucleation efficiencies, my company develops series of new DBS class polyolefin nucleating agent, can be widely used for polyacrylic transparent modified, it is effectively improved the transparency of PP product, it is adapted to various processing technique. and there is no special odor, can be used for the fields such as agricultural film, food containers, hold-up vessel, carafe, packaging film, CD box, auto parts and components.
Summary of the invention
The present invention has synthesized series of new DBS class polyolefin nucleating agent.
The novel DBS gellike factor, shown in its formula such as formula (I):
Wherein,
R1 is the saturated fat alkyl of the straight or branched of hydrogen or C1-C4;
M and n is the integer of 0-5, including 0,1,2,3,4,5.
The DBS class polyolefin nucleating agent of the present invention, differs from existing polyolefin nucleating agent on electronic structure, is effectively improved the transparency and the optical property of PP product, prepares commercially valuable new material.
The preparation method that present invention also offers above-mentioned DBS class polyolefin nucleating agent. Described method includes adopting alcohol as solvent, uses acidic catalyst and phase transfer catalyst, sorbitol and aldehyde reaction obtain DBS class polyolefin nucleating agent.
The preparation method of DBS class polyolefin nucleating agent of the present invention is preferably as follows states preparation method.
The preparation method of DBS class polyolefin nucleating agent as shown in formula (I), comprises the following steps:
A () adopts methanol as solvent, ortho acid trimethyl is acidic catalyst, and tetrabutyl ammonium bromide is phase transfer catalyst, and sorbitol and aldehyde reaction obtain DBS class polyolefin nucleating agent; Its reaction equation is as follows:
Polyolefinic crystallization behavior is had appreciable impact by gelator, and many materials all can as the nucleator of PP, but different nucleators has different nucleating effects. Promote that grainiess miniaturization is accelerated in PP crystallization by adding nucleator, improve the PP high performance that PP physical property is development in the recent period, the simple and efficient way of high transparency, nucleator affects the usual nucleation PP of its physical and mechanical property by change PP crystal habit and has higher hot strength and modulus, high heat distortion temperature, hardness and the transparency.
Above-mentioned DBS class polyolefin nucleating agent can be applied in polyolefin products manufacture as nucleator, its addition is the 0.1��2.0% of polyolefin quality, it is preferred to 0.1%, 0.2%, 0.5%, 0.6%, 0.8%, 1.2%, 1.4%%, 1.5%, 1.8%.
Industrially, adding nucleator is to accelerate polyolefinic overall crystallization rate, shortening the machine-shaping time and reduce the average-size of spherocrystal, thus improving polyolefinic mechanical performance and improving light transmittance and mist degree. Glucitol derivative is as a class organic nucleating agent DBS, for the high molecular nucleation highly significant of TPO. In the cooling procedure of molten condition, gelation is there is in DBS in polyolefinic melt, form a kind of huge network structure being made up of fento, very big surface area can be provided, and molecular polyolefin easily nucleation on DBS fento surface, so DBS has good nucleation for TPO macromolecule. Growing nonparasitically upon another plant crystallization relation it is generally believed that the mechanism of action of nucleator is one, namely macromolecule carries out epitaxial growth on the surface of small molecule crystals. The propositions such as Thierry nucleation efficiencies evaluates the nucleator influence degree to polyolefin crystallization behavior.
The present invention has positive effect: the nucleator that (1) present invention prepares is tasteless, is effectively improved the odor problem of existing nucleator; (2) nucleator of the present invention is effectively accelerated the crystallization rate of vistanex, is improved its degree of crystallinity, makes the polyolefinic transparency and lustrous surface increase, improves the physicochemical properties such as its bending modulus, tensile yield strength, heat distortion temperature and impact strength; (3) preparation method step of the present invention is succinct, it is easy to accomplish industrialized production.
Detailed description of the invention
(embodiment 1)
The synthesis of 1,3:2,4-bis-(the fluoro-4-t-butylbenzyl of 3-) sorbitol
50mL methanol is added in the four-hole boiling flask with thermometer and condensing reflux pipe, add 4.55g (25mmol) sorbitol, heating in water bath is to 50 DEG C, sorbitol all dissolves recession and dewaters bath, add 5.30g (50mmol) trimethyl orthoformate, 0.24g tetrabutyl tribromide ammonium, the fluoro-4-tert-butyl benzene formaldehyde of 50mmol3-, reacting under room temperature, TLC detects reaction. After 7h is stirred at room temperature, it is poured slowly in the NaOH solution that 100mL mass fraction is 5.0%, is washed to neutrality, then use 100mL methanol wash column, 70 DEG C of vacuum drying 5h.
1HNMR(CHCl3d3) �� ppm:7.20 (m, 2H, aromatic ring H) 6.88 (m, 2H, aromatic ring H), 6.82 (m, 2H, aromatic ring H), 5.98 (s, 2H, semialdehydeH), 4.44 (t, 2H), 4.19 (m, 1H), 3.81 (m, 4H), 3.62 (m, 1H), 1.34 (s, 18H, 6CH3)��
(embodiment 2)
The synthesis of 1,3:2,4-bis-(the fluoro-4-tert-Butyl-benzyI of 3,5-bis-) sorbitol
50mL methanol is added in the four-hole boiling flask with thermometer and condensing reflux pipe, add 4.55g (25mmol) sorbitol, heating in water bath is to 50 DEG C, sorbitol all dissolves recession and dewaters bath, adds 5.30g (50mmol) trimethyl orthoformate, 0.24g tetrabutyl tribromide ammonium, 50mmol3, the fluoro-4-tert-butyl benzene formaldehyde of 5-bis-, reacts under room temperature, and TLC detects reaction. After 7h is stirred at room temperature, it is poured slowly in the NaOH solution that 100mL mass fraction is 5.0%, is washed to neutrality, then use 100mL methanol wash column, 70 DEG C of vacuum drying 5h.
1HNMR(CHCl3d3) �� ppm:6.59 (s, 4H, aromatic ring H), 5.98 (s, 2H, semialdehydeH), 4.44 (t, 2H), 4.19 (m, 1H), 3.81 (m, 4H), 3.62 (m, 1H), 1.34 (s, 18H, 6CH3)��
(embodiment 3)
The synthesis of 1,3:2,4-bis-(the fluoro-4-ethyl-benzyl of 3,5-bis-) sorbitol
50mL methanol is added in the four-hole boiling flask with thermometer and condensing reflux pipe, add 4.55g (25mmol) sorbitol, heating in water bath is to 50 DEG C, sorbitol all dissolves recession and dewaters bath, adds 5.30g (50mmol) trimethyl orthoformate, 0.24g tetrabutyl tribromide ammonium, 50mmol3, the fluoro-4-ethylo benzene formaldehyde of 5-bis-, reacts under room temperature, and TLC detects reaction. After 7h is stirred at room temperature, it is poured slowly in the NaOH solution that 100mL mass fraction is 5.0%, is washed to neutrality, then use 100mL methanol wash column, 70 DEG C of vacuum drying 5h.
1HNMR(CHCl3d3) �� ppm:6.62 (m, 4H, aromatic ring H), 5.98 (s, 2H, semialdehydeH), 4.44 (t, 2H), 4.19 (m, 1H), 3.81 (m, 4H), 3.62 (m, 1H), 2.59 (m, 4H, 2CH 2 CH3),1.34(s,18H,6CH 3 )��
(embodiment 4)
The synthesis of 1,3:2,4-bis-(the fluoro-4-ethyl-benzyl of 3-) sorbitol
50mL methanol alcohol is added in the four-hole boiling flask with thermometer and condensing reflux pipe, add 4.55g (25mmol) sorbitol, heating in water bath is to 50 DEG C, sorbitol all dissolves recession and dewaters bath, add 5.30g (50mmol) trimethyl orthoformate, 0.24g tetrabutyl tribromide ammonium, the fluoro-4-ethylo benzene formaldehyde of 50mmol3-, reacting under room temperature, TLC detects reaction. After 7h is stirred at room temperature, it is poured slowly in the NaOH solution that 100mL mass fraction is 5.0%, is washed to neutrality, then use 100mL methanol wash column, 70 DEG C of vacuum drying 5h.
1HNMR(CHCl3d3) �� ppm:7.03 (m, 2H, aromatic ring H) 6.91 (m, 2H, aromatic ring H), 6.85 (m, 2H, aromatic ring H), 5.98 (s, 2H, semialdehydeH), 4.44 (t, 2H), 4.19 (m, 1H), 3.81 (m, 4H), 3.62 (m, 1H), 2.59 (m, 4H, 2CH 2 CH3),1.34(s,18H,6CH 3 )��
(embodiment 5)
The synthesis of 1,3:2,4-bis-(the fluoro-4-isopropyl-benzyl of 3-) sorbitol
50mL methanol alcohol is added in the four-hole boiling flask with thermometer and condensing reflux pipe, add 4.55g (25mmol) sorbitol, heating in water bath is to 50 DEG C, sorbitol all dissolves recession and dewaters bath, add 5.30g (50mmol) trimethyl orthoformate, 0.24g tetrabutyl tribromide ammonium, the fluoro-4-propylbenzyl aldehyde of 50mmol3-, reacting under room temperature, TLC detects reaction. After 7h is stirred at room temperature, it is poured slowly in the NaOH solution that 100mL mass fraction is 5.0%, is washed to neutrality, then use 100mL methanol wash column, 70 DEG C of vacuum drying 5h.
1HNMR(CHCl3d3) �� ppm:7.04 (m, 2H, aromatic ring H) 6.88 (m, 2H, aromatic ring H), 6.82 (m, 2H, aromatic ring H), 5.98 (s, 2H, semialdehydeH), 4.44 (t, 2H), 4.19 (m, 1H), 3.81 (m, 4H), 3.62 (m, 1H), 3.12 (m, 2H, 2CH(CH3)2),1.29(s,18H,6CH 3 )��
(embodiment 6)
The synthesis of 1,3:2,4-bis-(the fluoro-4-isopropyl-benzyl of 3,5-bis-) sorbitol
50mL methanol alcohol is added in the four-hole boiling flask with thermometer and condensing reflux pipe, add 4.55g (25mmol) sorbitol, heating in water bath is to 50 DEG C, sorbitol all dissolves recession and dewaters bath, adds 5.30g (50mmol) trimethyl orthoformate, 0.24g tetrabutyl tribromide ammonium, 50mmol3, the fluoro-4-propylbenzyl aldehyde of 5-bis-, reacts under room temperature, and TLC detects reaction. After 7h is stirred at room temperature, it is poured slowly in the NaOH solution that 100mL mass fraction is 5.0%, is washed to neutrality, then use 100mL methanol wash column, 70 DEG C of vacuum drying 5h.
1HNMR(CHCl3d3) �� ppm:6.59 (m, 4H, aromatic ring H), 5.98 (s, 2H, semialdehydeH), 4.44 (t, 2H), 4.19 (m, 1H), 3.81 (m, 4H), 3.62 (m, 1H), 3.12 (m, 2H, 2CH(CH3)2), 1.29(s,18H,6CH 3 )��
(embodiment 7)
The synthesis of 1,3:2,4-bis-(4-romethyl-benzy) sorbitol
50mL methanol alcohol is added in the four-hole boiling flask with thermometer and condensing reflux pipe, add 4.55g (25mmol) sorbitol, heating in water bath is to 50 DEG C, sorbitol all dissolves recession and dewaters bath, add 5.30g (50mmol) trimethyl orthoformate, 0.24g tetrabutyl tribromide ammonium, 50mmol4-trifluoromethylated benzaldehyde, reacting under room temperature, TLC detects reaction. After 7h is stirred at room temperature, it is poured slowly in the NaOH solution that 100mL mass fraction is 5.0%, is washed to neutrality, then use 100mL methanol wash column, 70 DEG C of vacuum drying 5h.
1HNMR(CHCl3d3) �� ppm:7.384 (m, 4H, aromatic ring H), 7.12 (m, 4H, aromatic ring H), 5.98 (s, 2H, semialdehydeH), 4.44 (t, 2H), 4.19 (m, 1H), 3.81 (m, 4H), 3.62 (m, 1H).
Particular embodiments described above; the purpose of the present invention, technical scheme and beneficial effect have been further described; it is it should be understood that; the foregoing is only specific embodiments of the invention; it is not limited to the present invention; all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (5)
1. a DBS class polyolefin nucleating agent, it is characterised in that shown in its formula such as formula (I):
Wherein,
R1 is the saturated fat alkyl of the straight or branched of hydrogen or C1-C4;
M and n is the integer of 0-5.
2. DBS class polyolefin nucleating agent according to claim 1, wherein said nucleator is one of the following: 1, 3:2, 4-bis-(the fluoro-4-t-butylbenzyl of 3-) sorbitol, 1, 3:2, 4-bis-(3, the fluoro-4-tert-Butyl-benzyI of 5-bis-) sorbitol, 1, 3:2, 4-bis-(3, the fluoro-4-ethyl-benzyl of 5-bis-) sorbitol, 1, 3:2, 4-bis-(the fluoro-4-ethyl-benzyl of 3-) sorbitol, 1, 3:2, 4-bis-(the fluoro-4-isopropyl-benzyl of 3-) sorbitol, 1, 3:2, 4-bis-(3, the fluoro-4-isopropyl-benzyl of 5-bis-) sorbitol, 1, 3:2, 4-bis-(4-romethyl-benzy) sorbitol, 1, 3:2, 4-bis-(3, 4, 5-trifluoro-benzvl) sorbitol, 1, 3:2, 4-bis-(2, 3, 4, 5, 6-PFBBR) sorbitol, 1, 3:2, 4-bis-(2-luorobenzyl) sorbitol, 1, 3:2, 4-bis-(2, 3, 4-trifluoro-benzyl) sorbitol, 1, 3:2, 4-bis-(2, 3, 5-trifluoro-benzyl) sorbitol, 1, 3:2, 4-bis-(2, 3, 6-trifluoro-benzyl) sorbitol, 1, 3:2, 4-bis-(2, 4, 5-trifluoro-benzyl) sorbitol, 1, 3:2, 4-bis-(2, 3, 4, 5-ptfe benzyl) sorbitol, 1, 3:2, 4-bis-(2, 3, 4, 6-ptfe benzyl) sorbitol, 1, 3:2, 4-bis-(2, 3, 5, 6-ptfe benzyl) sorbitol.
3. the method preparing DBS class polyolefin nucleating agent as claimed in claim 1 or 2, comprising: adopt alcohol as solvent, uses acidic catalyst and phase transfer catalyst, sorbitol and aldehyde reaction obtains DBS class polyolefin nucleating agent.
4. method according to claim 3, wherein adopting methanol as solvent, ortho acid trimethyl is acidic catalyst, and tetrabutyl ammonium bromide is phase transfer catalyst, and sorbitol and aldehyde reaction obtain DBS class polyolefin nucleating agent;
Its reaction equation is as follows:
5. the application of DBS class polyolefin nucleating agent according to claim 1 and 2, it is characterised in that: being applied in polyolefin products manufacture as nucleator, its addition is the 0.1��2.0% of polyolefin quality.
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Cited By (2)
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| CN108191882A (en) * | 2018-01-17 | 2018-06-22 | 泰山医学院 | A kind of preparation method of polyol acetal class compound |
| CN115286840A (en) * | 2022-08-05 | 2022-11-04 | 中化石化销售有限公司 | Sorbitol compound nucleating agent, polypropylene material, preparation method and application thereof |
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| CN1460107A (en) * | 2000-09-01 | 2003-12-03 | 美利肯公司 | Fluorinated and alkylated alditol derivatives and polyolefin articles containing same |
| CN1514717A (en) * | 2001-03-23 | 2004-07-21 | 美利肯公司 | Asymmetric benzaldehyde alditol derivatives, methods of making thereof, and compositions and articles containing same |
| CN1524108A (en) * | 2001-07-03 | 2004-08-25 | Clarifying agent formulations for thermoplastics exhibiting very high nucleation efficacy |
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| CN1460107A (en) * | 2000-09-01 | 2003-12-03 | 美利肯公司 | Fluorinated and alkylated alditol derivatives and polyolefin articles containing same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108191882A (en) * | 2018-01-17 | 2018-06-22 | 泰山医学院 | A kind of preparation method of polyol acetal class compound |
| CN115286840A (en) * | 2022-08-05 | 2022-11-04 | 中化石化销售有限公司 | Sorbitol compound nucleating agent, polypropylene material, preparation method and application thereof |
| CN115286840B (en) * | 2022-08-05 | 2024-04-16 | 中化石化销售有限公司 | Sorbitol compound nucleating agent, polypropylene material, preparation method and application thereof |
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