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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- 239000002667 nucleating agent Substances 0.000 title claims abstract description 53
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 46
- 239000000600 sorbitol Substances 0.000 claims abstract description 46
- -1 3-fluoro-4- tertiary butyl benzyl Chemical group 0.000 claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000001318 4-trifluoromethylbenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])*)C(F)(F)F 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000002905 orthoesters Chemical class 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- TVSLNRQODQRVJZ-UHFFFAOYSA-N 2-(3,4,5-trifluorophenyl)acetonitrile Chemical group FC1=CC(CC#N)=CC(F)=C1F TVSLNRQODQRVJZ-UHFFFAOYSA-N 0.000 claims 1
- 125000004847 2-fluorobenzyl group Chemical group [H]C1=C([H])C(F)=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 9
- 230000008025 crystallization Effects 0.000 abstract description 9
- 229920005672 polyolefin resin Polymers 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000005022 packaging material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 35
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 22
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000004743 Polypropylene Substances 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 14
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- SFLXUZPXEWWQNH-UHFFFAOYSA-K tetrabutylazanium;tribromide Chemical compound [Br-].[Br-].[Br-].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC SFLXUZPXEWWQNH-UHFFFAOYSA-K 0.000 description 7
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229920001410 Microfiber Polymers 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- 239000003658 microfiber Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 1
- QWNAGJLCKLCPTR-UHFFFAOYSA-N 3-fluoro-4-propan-2-ylbenzaldehyde Chemical compound CC(C)C1=CC=C(C=O)C=C1F QWNAGJLCKLCPTR-UHFFFAOYSA-N 0.000 description 1
- BEOBZEOPTQQELP-UHFFFAOYSA-N 4-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=C(C=O)C=C1 BEOBZEOPTQQELP-UHFFFAOYSA-N 0.000 description 1
- VWIXGSHCRPUMFL-UHFFFAOYSA-N 4-ethyl-3-fluorobenzaldehyde Chemical compound CCC1=CC=C(C=O)C=C1F VWIXGSHCRPUMFL-UHFFFAOYSA-N 0.000 description 1
- LDRUWSURFNHZRE-UHFFFAOYSA-N 4-tert-butyl-3-fluorobenzaldehyde Chemical compound CC(C)(C)C1=CC=C(C=O)C=C1F LDRUWSURFNHZRE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
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 invention relates to a DBS polyolefin nucleating agent, a preparation method and application thereof.
Background
In recent years, with the rapid increase in the production of polyolefin resins, the field of processing applications thereof has become more and more widespread. The requirements of people on plastic products are increasingly strict while the living standard of people is continuously improved. The nucleating agent is used as an excellent modification auxiliary agent of polyolefin, and can greatly reduce the haze of a plastic product, improve the transparency and the heat distortion temperature, improve the strength of the product, greatly improve the application performance of the product and finally improve the added value of the product. Its development and application has attracted general attention from countries around the world.
The chemical structure of the polyolefin nucleating agent can be divided into three types, namely inorganic nucleating agent, organic nucleating agent and high polymer nucleating agent, wherein the organic nucleating agent has the best nucleating modification effect and use performance and is the most active and widely used nucleating agent in research. The organic nucleating agent is an organic compound with lower relative molecular mass, and mainly comprises nucleating agents such as dibenzylidene sorbitol and derivatives thereof, carboxylic acid and metal salts thereof, organic phosphate metal salts, amides and the like.
The development and research of the dibenzylidene sorbitol and the homologous derivative nucleating agent thereof are hot areas of domestic and foreign research in recent years. Since the first Japanese patent of industrial significance was made in 1972, the synthesis technology of such nucleating agents has been greatly developed.
In the 70 s of the 20 th century, Hamad of Japanese discovered that adding dibenzylidene sorbitol (DBS) to PP can improve the transparency and glossiness of PP, improve the heat distortion temperature and rigidity of PP, accelerate the crystallization speed of PP and shorten the molding processing period. Since then, this PP modification technology has become widespread worldwide and has been commercially available in the 80 s of the 20 th century.
The nucleating agents of the homologous derivatives of Millad3905, Millad3940 and Millad3988 are successively developed and successfully put on the market by Milliken chemical company in the United states, and a better application effect is achieved. DBS and 5 brands of products of homologous derivatives thereof are developed and put on the market successively by petrochemical research institute of Lanzhou petrochemical company, and good application effect is achieved.
However, the polyolefin nucleating agent on the market at present has the defects of large smell, low improved transparency, low nucleating efficiency and the like, and a series of novel DBS polyolefin nucleating agents are developed by the company, can be widely used for transparent modification of polypropylene, effectively improve the transparency of PP (polypropylene) products, are suitable for various processing technologies, have no special smell, and can be used in the fields of agricultural films, food containers, storage containers, beverage bottles, packaging films, CD (compact disc) boxes, automobile parts and the like.
Disclosure of Invention
The invention synthesizes a series of novel DBS polyolefin nucleating agents.
The novel DBS gelator has a general formula shown in formula (I):
wherein,
r1 is hydrogen or a C1-C4 straight or branched chain saturated aliphatic hydrocarbon group;
m and n are integers from 0 to 5, including 0, 1, 2,3,4, 5.
The DBS polyolefin nucleating agent is different from the existing polyolefin nucleating agent in electronic structure, effectively improves the transparency and optical performance of PP products, and prepares a novel material with commercial value.
The invention also provides a preparation method of the DBS polyolefin nucleating agent. The method comprises the step of reacting sorbitol with aldehyde by using alcohol as a solvent and using an acid catalyst and a phase transfer catalyst to obtain the DBS polyolefin nucleating agent.
The process for preparing the DBS polyolefin nucleating agent of the present invention is preferably as follows.
The preparation method of the DBS polyolefin nucleating agent shown in the formula (I) comprises the following steps:
(a) adopting methanol as a solvent, trimethyl orthoester as an acidic catalyst, tetrabutylammonium bromide as a phase transfer catalyst, and reacting sorbitol with aldehyde to obtain the DBS polyolefin nucleating agent; the reaction equation is as follows:
the gelator has a significant influence on the crystallization behavior of polyolefins, and many substances can be used as nucleating agents for PP, however, different nucleating agents have different nucleating effects. The addition of nucleating agent to promote PP crystallization to accelerate grain structure micronization and improve PP physical properties is a simple and effective method for recently developed PP high performance and high transparency, and the nucleating agent influences the physical and mechanical properties of PP by changing the crystallization form of PP, so that the nucleated PP has higher tensile strength and modulus, high heat distortion temperature, hardness and transparency.
The DBS polyolefin nucleating agent can be used as a nucleating agent in the production of polyolefin products, and the adding amount of the DBS polyolefin nucleating agent is 0.1-2.0% of the mass of polyolefin, preferably 0.1%, 0.2%, 0.5%, 0.6%, 0.8%, 1.2%, 1.4%, 1.5% and 1.8%.
Industrially, the nucleating agent is added to accelerate the overall crystallization speed of polyolefin, shorten the process molding time and reduce the average size of spherulites, thereby improving the mechanical properties of polyolefin and improving light transmittance and haze. The sorbitol derivative is used as an organic nucleating agent DBS, and has a very obvious nucleating effect on polyolefin macromolecules. During the cooling process in the molten state, DBS is gelated in the melt of polyolefin to form a huge reticular structure consisting of microfibers, so that a large surface area can be provided, and polyolefin molecules are easy to nucleate on the surfaces of the DBS microfibers, so that the DBS has a good nucleating effect on polyolefin polymers. It is believed that the mechanism of action of nucleating agents is an epitaxial crystallization relationship, i.e., the epitaxial growth of macromolecules on the surface of small molecule crystals. Thiierry et al propose to evaluate the extent of the nucleating agent's effect on polyolefin crystallization behavior using nucleation efficiency.
The invention has the positive effects that: (1) the nucleating agent prepared by the invention is tasteless, and effectively solves the problem of odor of the existing nucleating agent; (2) the nucleating agent of the invention effectively accelerates the crystallization speed of polyolefin resin, improves the crystallinity of the polyolefin resin, increases the transparency and surface gloss of the polyolefin, and improves the physical and chemical properties of the polyolefin resin, such as flexural modulus, tensile yield strength, thermal deformation temperature, impact strength and the like; (3) the preparation method provided by the invention is simple in steps and easy to realize industrial production.
Detailed Description
(example 1)
Synthesis of 1,3:2, 4-bis (3-fluoro-4-tert-butylbenzyl) sorbitol
Adding 50mL of methanol into a four-neck flask with a thermometer and a condensing reflux pipe, adding 4.55g (25mmol) of sorbitol, heating the mixture in a water bath to 50 ℃, removing the water bath after the sorbitol is completely dissolved, adding 5.30g (50mmol) of trimethyl orthoformate, 0.24g of tetrabutylammonium tribromide and 50mmol of 3-fluoro-4-tert-butylbenzaldehyde, reacting at room temperature, and detecting the reaction by TLC. After stirring for 7h at room temperature, slowly pouring the mixture into 100mL of NaOH solution with the mass fraction of 5.0%, washing the mixture to be neutral by water, then washing the mixture by using 100mL of methanol, and drying the mixture for 5h in vacuum at 70 ℃.
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,6 CH)3)。
(example 2)
Synthesis of 1,3:2, 4-bis (3, 5-difluoro-4-tert-butyl-benzyl) sorbitol
Adding 50mL of methanol into a four-neck flask with a thermometer and a condensing reflux pipe, adding 4.55g (25mmol) of sorbitol, heating the mixture in a water bath to 50 ℃, removing the water bath after the sorbitol is completely dissolved, adding 5.30g (50mmol) of trimethyl orthoformate, 0.24g of tetrabutylammonium tribromide and 50mmol of 3, reacting at room temperature, and detecting the reaction by TLC. After stirring for 7h at room temperature, slowly pouring the mixture into 100mL of NaOH solution with the mass fraction of 5.0%, washing the mixture to be neutral by water, then washing the mixture by using 100mL of methanol, and drying the mixture for 5h in vacuum at 70 ℃.
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,6 CH)3)。
(example 3)
Synthesis of 1,3:2, 4-bis (3, 5-difluoro-4-ethyl-benzyl) sorbitol
50mL of methanol was put in a four-necked flask equipped with a thermometer and a reflux condenser, 4.55g (25mmol) of sorbitol was added, the mixture was heated in a water bath to 50 ℃ and the water bath was removed after the sorbitol was completely dissolved, 5.30g (50mmol) of trimethyl orthoformate, 0.24g of tetrabutylammonium tribromide, 50mmol of 3, 5-difluoro-4-ethylbenzaldehyde were added, and the reaction was carried out at room temperature by TLC. After stirring for 7h at room temperature, slowly pouring the mixture into 100mL of NaOH solution with the mass fraction of 5.0%, washing the mixture to be neutral by water, then washing the mixture by using 100mL of methanol, and drying the mixture for 5h in vacuum at 70 ℃.
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)H),2.59(m,4H,2CH 2 CH3),1.34(s,18H,6CH 3 )。
(example 4)
Synthesis of 1,3:2, 4-bis (3-fluoro-4-ethyl-benzyl) sorbitol
50mL of methanol was put into a four-necked flask equipped with a thermometer and a reflux condenser, 4.55g (25mmol) of sorbitol was added, the mixture was heated in a water bath to 50 ℃ and the water bath was removed after the sorbitol was completely dissolved, 5.30g (50mmol) of trimethyl orthoformate, 0.24g of tetrabutylammonium tribromide, 50mmol of 3-fluoro-4-ethylbenzaldehyde were added, and the reaction was carried out at room temperature and detected by TLC. After stirring for 7h at room temperature, slowly pouring the mixture into 100mL of NaOH solution with the mass fraction of 5.0%, washing the mixture to be neutral by water, then washing the mixture by using 100mL of methanol, and drying the mixture for 5h in vacuum at 70 ℃.
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, 2H)CH 2 CH3),1.34(s,18H,6CH 3 )。
(example 5)
Synthesis of 1,3:2, 4-bis (3-fluoro-4-isopropyl-benzyl) sorbitol
Adding 50mL of methanol into a four-neck flask with a thermometer and a condensing reflux pipe, adding 4.55g (25mmol) of sorbitol, heating the mixture in a water bath to 50 ℃, removing the water bath after the sorbitol is completely dissolved, adding 5.30g (50mmol) of trimethyl orthoformate, 0.24g of tetrabutylammonium tribromide and 50mmol of 3-fluoro-4-isopropylbenzaldehyde, reacting at room temperature, and detecting the reaction by TLC. After stirring for 7h at room temperature, slowly pouring the mixture into 100mL of NaOH solution with the mass fraction of 5.0%, washing the mixture to be neutral by water, then washing the mixture by using 100mL of methanol, and drying the mixture for 5h in vacuum at 70 ℃.
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)H),3.12(m,2H,2CH(CH3)2),1.29(s,18H,6CH 3 )。
(example 6)
Synthesis of 1,3:2, 4-bis (3, 5-difluoro-4-isopropyl-benzyl) sorbitol
Adding 50mL of methanol into a four-neck flask with a thermometer and a condensing reflux pipe, adding 4.55g (25mmol) of sorbitol, heating the mixture in a water bath to 50 ℃, removing the water bath after the sorbitol is completely dissolved, adding 5.30g (50mmol) of trimethyl orthoformate, 0.24g of tetrabutylammonium tribromide and 50mmol of 3, reacting 5-difluoro-4-isopropylbenzaldehyde at room temperature, and detecting the reaction by TLC. After stirring for 7h at room temperature, slowly pouring the mixture into 100mL of NaOH solution with the mass fraction of 5.0%, washing the mixture to be neutral by water, then washing the mixture by using 100mL of methanol, and drying the mixture for 5h in vacuum at 70 ℃.
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)CH(CH3)2),1.29(s,18H,6CH 3 )。
(example 7)
Synthesis of 1,3:2, 4-bis (4-trifluoromethyl-benzyl) sorbitol
50mL of methanol was put into a four-necked flask equipped with a thermometer and a reflux condenser, 4.55g (25mmol) of sorbitol was added, the mixture was heated in a water bath to 50 ℃ and the water bath was removed after the sorbitol was completely dissolved, 5.30g (50mmol) of trimethyl orthoformate, 0.24g of tetrabutylammonium tribromide, 50mmol of 4-trifluoromethylbenzaldehyde were added, and the reaction was carried out at room temperature by TLC. After stirring for 7h at room temperature, slowly pouring the mixture into 100mL of NaOH solution with the mass fraction of 5.0%, washing the mixture to be neutral by water, then washing the mixture by using 100mL of methanol, and drying the mixture for 5h in vacuum at 70 ℃.
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).
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A DBS polyolefin nucleating agent is characterized in that the general formula is shown as the formula (I):
wherein,
r1 is hydrogen or a C1-C4 straight or branched chain saturated aliphatic hydrocarbon group;
m and n are integers from 0 to 5.
2. The DBS polyolefin nucleating agent of claim 1, wherein the nucleating agent is one of: 1,3:2, 4-bis (3-fluoro-4-tert-butylbenzyl) sorbitol, 1,3:2, 4-bis (3, 5-difluoro-4-ethyl-benzyl) sorbitol, 1,3:2, 4-bis (3-fluoro-4-isopropyl-benzyl) sorbitol, 1,3:2, 4-bis (3, 5-difluoro-4-isopropyl-benzyl) sorbitol, 1,3:2, 4-bis (4-trifluoromethyl-benzyl) sorbitol, 1,3:2, 4-bis (3,4, 5-trifluoro-benzyl) sorbitol, 1,3:2, 4-bis (2,3,4,5, 6-pentafluorobenzyl) sorbitol, 1,3:2, 4-bis (2-fluorobenzyl) sorbitol, 1,3:2, 4-bis (2,3, 4-trifluorobenzyl) sorbitol, 1,3:2, 4-bis (2,3, 5-trifluorobenzyl) sorbitol, 1,3:2, 4-bis (2,3, 6-trifluorobenzyl) sorbitol, 1,3:2, 4-bis (2,4, 5-trifluorobenzyl) sorbitol, 1,3:2, 4-bis (2,3,4, 5-tetrafluorobenzyl) sorbitol, 1,3:2, 4-bis (2,3,4, 6-tetrafluorobenzyl) sorbitol, 1,3:2, 4-bis (2,3,5, 6-tetrafluorobenzyl) sorbitol.
3. A process for preparing a DBS-based polyolefin nucleating agent as defined in claim 1 or 2, comprising: alcohol is used as a solvent, and sorbitol and aldehyde are reacted by using an acid catalyst and a phase transfer catalyst to obtain the DBS polyolefin nucleating agent.
4. The method as claimed in claim 3, wherein methanol is used as solvent, trimethyl orthoester is used as acidic catalyst, tetrabutylammonium bromide is used as phase transfer catalyst, sorbitol reacts with aldehyde to obtain DBS polyolefin nucleating agent;
the reaction equation is as follows:
5. use of a DBS polyolefin nucleating agent according to claim 1 or 2, characterized in that: the nucleating agent is applied to the preparation of polyolefin products, and the addition amount of the nucleating agent is 0.1-2.0% of the mass of polyolefin.
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