CN110343290A - Composite nucleating agent and its preparation method and application - Google Patents
Composite nucleating agent and its preparation method and application Download PDFInfo
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- CN110343290A CN110343290A CN201910674014.4A CN201910674014A CN110343290A CN 110343290 A CN110343290 A CN 110343290A CN 201910674014 A CN201910674014 A CN 201910674014A CN 110343290 A CN110343290 A CN 110343290A
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- China
- Prior art keywords
- nucleating agent
- composite nucleating
- benzoate
- carboxylic acid
- acid salt
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- 239000002667 nucleating agent Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- -1 bicyclic carboxylic acid salt Chemical class 0.000 claims abstract description 55
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 20
- 239000002585 base Substances 0.000 claims description 18
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 11
- 235000010234 sodium benzoate Nutrition 0.000 claims description 11
- 239000004299 sodium benzoate Substances 0.000 claims description 11
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- LCGUMNBBTZIUES-UHFFFAOYSA-L disodium;2-butyl-3-methylbutanedioate Chemical compound [Na+].[Na+].CCCCC(C([O-])=O)C(C)C([O-])=O LCGUMNBBTZIUES-UHFFFAOYSA-L 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 5
- 229910001424 calcium ion Chemical group 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 6
- 229940050390 benzoate Drugs 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 125000002619 bicyclic group Chemical group 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- DGBKTJIQJQNAIN-UHFFFAOYSA-N 2-butyl-3-methylbutanedioic acid Chemical class CCCCC(C(O)=O)C(C)C(O)=O DGBKTJIQJQNAIN-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- XDIAMRVROCPPBK-UHFFFAOYSA-N 2,2-dimethylpropan-1-amine Chemical compound CC(C)(C)CN XDIAMRVROCPPBK-UHFFFAOYSA-N 0.000 description 1
- XETWSHBZXXVAQP-UHFFFAOYSA-N C(C(C)C)OC(C(C)(C)C)(OOCCC(C)C)OCCCCC Chemical compound C(C(C)C)OC(C(C)(C)C)(OOCCC(C)C)OCCCCC XETWSHBZXXVAQP-UHFFFAOYSA-N 0.000 description 1
- DUUFVWIKTVQSCG-UHFFFAOYSA-N CC(=C)C.[O] Chemical compound CC(=C)C.[O] DUUFVWIKTVQSCG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- CYFIAZRQBMLSRC-UHFFFAOYSA-N [Na].[Na].C(CCCCCC)(C(=O)O)C(=O)O Chemical compound [Na].[Na].C(CCCCCC)(C(=O)O)C(=O)O CYFIAZRQBMLSRC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- IMXLQXHCHYKEEE-UHFFFAOYSA-N benzene;formic acid Chemical class OC=O.C1=CC=CC=C1 IMXLQXHCHYKEEE-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- IZPNTDOWOBGHEG-UHFFFAOYSA-M sodium benzene formate Chemical compound [Na+].[O-]C=O.C1=CC=CC=C1 IZPNTDOWOBGHEG-UHFFFAOYSA-M 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of composite nucleating agents and its preparation method and application.Composite nucleating agent includes bicyclic carboxylic acid salt A and benzoate B.Composite nucleating agent of the invention can take into account the mechanical property and optical property of thermoplastic resin.
Description
Technical field
It is especially a kind of for thermoplastic resin the present invention relates to a kind of composite nucleating agent and its preparation method and application
Composite nucleating agent and its preparation method and application.
Background technique
Thermoplastic resin indicates that heating can melt, but cooling can keep solid polymer material.Thermoplastic resin packet
The polymer for showing crystallization or hypocrystalline form is included, specific example includes but is not limited to polyethylene, polypropylene, polybutene etc.
Polyolefin, the polyamide such as nylon66 fiber, polyurethanes, the polyester such as polyethylene terephthalate.
Thermoplastic resin can be used for storage container, medical instrument, food packaging, plastic pipe, frame component.Thermoplasticity
The process of resin is extremely important for its performance.Under normal conditions, the thermoplastic resin composition containing nucleating agent has
Faster crystallization rate.The compound for providing fast crystallization rate and/or high polymer crystallization temperature is usually known as nucleating agent.Have
The durability of thermoplastic resin, impact resistance etc. can be improved in a little nucleating agents.
CN101613490B discloses a kind of polyolefin resin nucleating agent, for two acetals of polyalcohol-Silicage-polymer- bonded phase
Object.
CN101987891B discloses a kind of composition containing polyolefin resin and nucleating agent, and the nucleating agent is polynary
Two acetals of alcohol-Silicage-polymer- bonded phase object.The nucleating agent significantly improves the mechanical performance and hot property of polyolefin resin.Above-mentioned patent text
It offers and does not fully consider mechanical property and optical property.
CN1524108B discloses a kind of thermoplastic additive, including two rings [2.2.1] heptane -2,3- dicarboxylic acids two
Sodium and certain benzylidene sorbitol acetals.The additive generates low transparency and high nucleation efficiencies simultaneously.Above patent document
Do not fully consider mechanical property and optical property.In addition, the patent document thinks most of typical nucleating compound (such as benzene first
Sour sodium, bicyclic [2.2.1] heptane dicarboxylic acid disodium) polyolefin articles nucleation efficiencies can be reduced, thus it is unfavorable for its comprehensive performance
Raising.
Summary of the invention
In view of this, heat can be taken into account it is an object of the present invention to the composite nucleating agent for thermoplastic resin
The mechanical property and optical property of plastic resin.It is another object of the present invention to provide the preparation sides of above-mentioned composite nucleating agent
Method.It is yet a further object of the present invention to provide the purposes of above-mentioned composite nucleating agent.The present invention adopts the following technical scheme that realization
Above-mentioned purpose.
On the one hand, the present invention provides a kind of composite nucleating agent for thermoplastic resin, including bicyclic carboxylic shown in formula (I)
Hydrochlorate A and benzoate B:
Wherein, R1~R10Separately it is selected from hydrogen, C1~C6 alkyl, hydroxyl, C1~C6 alkoxy, C2~C6 alkene oxygen
Base, amido, C1~C6 alkylamino radical, halogen, phenyl or alkane phenyl, M are selected from alkali metal ion or alkaline-earth metal ions；
Wherein, bicyclic carboxylic acid salt A and benzoate B weight ratio are 7:3~9:1.
Composite nucleating agent according to the present invention, it is preferable that the composite nucleating agent is by bicyclic carboxylic acid salt A and benzoate B group
At.
Composite nucleating agent according to the present invention, it is preferable that R1~R10Separately selected from hydrogen, C1~C3 alkyl, hydroxyl,
C1~C3 alkoxy, C2~C3 alkenyloxy group, amido, C1~C3 alkylamino radical, halogen, phenyl or alkane phenyl.
Composite nucleating agent according to the present invention, it is preferable that M is sodium ion or calcium ion.
Composite nucleating agent according to the present invention, it is preferable that bicyclic carboxylic acid salt A is two rings [2.2.1] heptane -2,3- dicarboxylic acids
Disodium salt.
Composite nucleating agent according to the present invention, it is preferable that benzoate B is the alkali metal salt of benzoic acid.
Composite nucleating agent according to the present invention, it is preferable that bicyclic carboxylic acid salt A is two rings [2.2.1] heptane -2,3- dicarboxylic acids
Disodium salt, benzoate B are sodium benzoate.
Composite nucleating agent according to the present invention, it is preferable that bicyclic carboxylic acid salt A and benzoate B weight ratio be 7:3,8:2 or
9:1。
On the other hand, the present invention provides the preparation method of above-mentioned composite nucleating agent, by bicyclic carboxylic acid salt A and benzoate B
It is dispersed in water, is sufficiently mixed the two until all dissolutions, then dry and crushing, obtain composite nucleating agent.
In another aspect, the present invention provides above-mentioned composite nucleating agent in the mechanical property and transparency for improving thermoplastic resin
Purposes.
The two nucleating agent is combined and is used by the present invention, it has unexpectedly been found that, the composite nucleating agent of specific proportion can improve
The mechanical property of thermoplastic resin, and its transparent performance can be improved.Preferred technical solution according to the present invention, of the invention answers
Synthetic kernel agent can significantly improve the bending modulus of thermoplastic resin, while can reduce the mist degree of thermoplastic resin.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, but protection scope of the present invention is not limited to
This.
In the present invention, thermoplastic resin indicates that heating can melt, but cooling can keep solid polymer material；Packet
Include but be not limited to polyolefin, polyamide, polyurethanes or polyester etc..
Composite nucleating agent for thermoplastic resin of the invention includes bicyclic carboxylic acid salt A and benzoate B.In certain realities
It applies in scheme, which is made of bicyclic carboxylic acid salt A and benzoate B.Bicyclic carboxylic acid salt A and benzoate B weight
Than for 7:3~9:1；Preferably 8:2~9:1.Mechanical property and optical property can be taken into account in this way.Specifically, bicyclic carboxylic acid salt A
It is 7:3,8:2 or 9:1 with benzoate B weight ratio.A preferred embodiment according to the present invention, bicyclic carboxylic acid salt A and benzene
Formates B weight ratio is 8:2.Mechanical property and optical property can be made to reach optimum balance state in this way.
Shown in bicyclic carboxylic acid salt A such as formula (I):
The main structure of bicyclic carboxylic acid salt A is bicyclic, and there are two carboxyl or carboxylates for band.Nuclearity is not being influenced into
In the case where, it is bicyclic on hydrogen atom can be replaced any other group.
In formula (I), R1~R10Separately it is selected from hydrogen, C1~C6 alkyl, hydroxyl, C1~C6 alkoxy, C2~C6
Alkenyloxy group, amido, C1~C6 alkylamino radical, halogen, phenyl or alkane phenyl.Preferably, R1~R10Separately selected from hydrogen, C1~
C3 alkyl, hydroxyl, C1~C3 alkoxy, C2~C3 alkenyloxy group, amido, C1~C3 alkylamino radical, halogen, phenyl or alkane phenyl.More
Preferably, R1~R10Separately selected from hydrogen, C1~C2 alkyl, hydroxyl, C1~C2 alkoxy, C2~C3 alkenyloxy group, amido,
C1~C2 alkylamino radical, halogen, phenyl or C1~C6 alkane phenyl.
The example of C1~C6 alkyl includes but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, just
Amyl, isopentyl, neopentyl, n-hexyl or isohesyl etc.；Preferably methyl, ethyl, n-propyl or isopropyl；More preferably first
Base.
The example of C1~C6 alkoxy includes but is not limited to methoxyl group, ethyoxyl, positive propoxy, isopropoxy, positive fourth oxygen
Base, isobutoxy, n-pentyloxy, isoamoxy, neopentyl oxygen, positive hexyloxy or dissident's oxygroup etc.；Preferably methoxyl group, ethoxy
Base, positive propoxy or isopropoxy；More preferably methoxyl group.
The example of C2~C6 alkenyloxy group includes but is not limited to ethyleneoxy, propenyloxy group, n-butene oxygroup, isobutene oxygen
Base, n-pentene oxygroup, isoamyl alkenyloxy group, n-hexylene oxygroup or dissident's alkenyloxy group etc.；Preferably ethyleneoxy, positive propenyloxy group or
Isopropyl alkenyloxy group；More preferably ethyleneoxy.
The example of C1~C6 alkylamino radical includes but is not limited to methylamino, ethylamino-, n-propylamine base, isopropylamine base, n-butylamine
Base, isobutyl amine, n-amylamine base, isoamyl amido, neopentyl amine base, n-hexylamine base or dissident's amido etc.；Preferably methylamino, ethamine
Base, n-propylamine base or isopropylamine base；More preferably methylamino.
The example of alkane phenyl includes but is not limited to tolyl, ethylbenzene, n-proplbenzene base, cumenyl, n-butyl benzene base, isobutyl
Phenyl, positive penta phenyl, isoamyl phenyl, new penta phenyl, just own phenyl or dissident's phenyl etc.；Preferably tolyl, ethylbenzene, positive third
Phenyl or cumenyl；More preferably tolyl.
M is selected from alkali metal ion or alkaline-earth metal ions；Preferably alkali metal ion.Alkali metal ion can selected from sodium from
Son, lithium ion, potassium ion etc., preferably sodium ion.Alkaline-earth metal ions can be selected from magnesium ion, calcium ion, barium ions etc.；It is excellent
It is selected as calcium ion.According to embodiment of the present invention, M is sodium ion or calcium ion.
In the present invention, bicyclic carboxylic acid salt A can be selected from two rings [2.2.1] heptane -2,3- dicarboxylate and its derivative.
Specifically, bicyclic carboxylic acid salt A can be selected from two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium salt or two rings [2.2.1] heptane -
2,3- dicarboxyl acid calcium salt.Bicyclic carboxylic acid salt A can be adopted to be obtained with the conventional methods in the field, such as disclosed in CN102952010B
Method.
In the present invention, benzoate B is the alkali metal salt of benzoic acid.The example of benzoate B includes but is not limited to benzene
Sodium formate, Potassium Benzoate etc.；Preferably sodium benzoate.
A specific embodiment according to the present invention, bicyclic carboxylic acid salt A are two rings [2.2.1] heptane -2,3- dicarboxylic acids
Disodium salt, benzoate B are sodium benzoate.The weight ratio of two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium salt and sodium benzoate
For 7:3~9:1；Preferably 8:2~9:1.Bending modulus can be improved in this way, and reduce mist degree.Two rings [2.2.1] heptane -2,
The weight ratio of 3- dicarboxylic acid disodium salt and sodium benzoate is 7:3,8:2 or 9:1.A preferred embodiment according to the present invention,
The weight ratio of two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium salt and sodium benzoate is 8:2.It can make bending modulus in this way
Reach optimum balance state with mist degree.
The preparation method of composite nucleating agent of the invention includes the following steps: to disperse bicyclic carboxylic acid salt A and benzoate B
In water, it is sufficiently mixed the two until all dissolutions, then dry and crushing, obtain composite nucleating agent.The dosage of water is not
There is special limitation.Dry and pulverization conditions are normal condition, and which is not described herein again.
In addition, the present invention also provides above-mentioned composite nucleating agents in the mechanical property and transparency for improving thermoplastic resin
Purposes.Thermoplastic resin indicates that heating can melt, but cooling can keep solid polymer material；Including but not limited to polyene
Hydrocarbon, polyamide, polyurethanes or polyester etc..Thermoplastic resin is preferably polyolefin, can farthest be played in this way
The effect of composite nucleating agent.Therefore, the present invention also provides above-mentioned composite nucleating agents to improve the mechanical property of polyolefin and transparent
Purposes in degree.
Examples 1 to 3
Two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium salt and sodium benzoate are dispersed in water, the two is sufficiently mixed
Until all dissolutions, then dry and crushing, obtain composite nucleating agent.Specific proportion is referring to table 1.
Table 1
| Serial number | Two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium salt/g | Sodium benzoate/g |
| 1 | 7 | 3 |
| 2 | 8 | 2 |
| 3 | 9 | 1 |
Comparative example 1~6
Two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium salt and sodium benzoate are dispersed in water, the two is sufficiently mixed
Until all dissolutions, then dry and crushing, obtain composite nucleating agent.Specific proportion is referring to table 2.
Table 2
| Serial number | Two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium salt/g | Sodium benzoate/g |
| 1 | 0 | 10 |
| 2 | 1 | 9 |
| 3 | 2 | 8 |
| 4 | 3 | 7 |
| 5 | 4 | 6 |
| 6 | 5 | 5 |
Experimental example
The composite nucleating agent of Examples 1 to 3 and comparative example 1~6 is added in acrylic resin.With polyacrylic weight
On the basis of, composite nucleating agent dosage is 0.56 ‰, and antioxidant 1010 dosage is 0.5 ‰, and irgasfos 168 dosage is 0.5 ‰, deacidification
Agent calcium stearate dosage is 0.5 ‰.
Concrete technology condition are as follows:
Each portion's temperature of extruder: 1 section, 190 DEG C；2 sections, 199 DEG C；3 sections, 212 DEG C；4 sections, 222 DEG C；5 sections, 221 DEG C；6 sections,
222℃。
Melt temperature: 235 DEG C；
Screw speed: 30Hz；
Rate of feeding: 40rpm
Head pressure: 1.1-1.2MPa.
It is granulated after mixture is melted, measures the performance of modified acrylic resin, be detailed in following table.Wherein, bending die
Amount is measured using GB/T 9341-2008 or ISO178:2001.Mist degree is measured using GB/T 2410-2008.
Table 3
| Serial number | Bending modulus/MPa | Mist degree/% |
| Embodiment 1 | 1250 | 30.3 |
| Embodiment 2 | 1270 | 28.4 |
| Embodiment 3 | 1275 | 29.6 |
| Comparative example 1 | 1190 | 35.9 |
| Comparative example 2 | 1200 | 42.8 |
| Comparative example 3 | 1190 | 39.8 |
| Comparative example 4 | 1210 | 39.8 |
| Comparative example 5 | 1200 | 34.4 |
| Comparative example 6 | 1210 | 33.9 |
Present invention is not limited to the embodiments described above, without departing from the essence of the present invention, this field skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (10)
1. a kind of composite nucleating agent for thermoplastic resin, including bicyclic carboxylic acid salt A shown in formula (I) and benzoate B:
Wherein, R1~R10Separately it is selected from hydrogen, C1~C6 alkyl, hydroxyl, C1~C6 alkoxy, C2~C6 alkenyloxy group, amine
Base, C1~C6 alkylamino radical, halogen, phenyl or alkane phenyl, M are selected from alkali metal ion or alkaline-earth metal ions；
Wherein, bicyclic carboxylic acid salt A and benzoate B weight ratio are 7:3~9:1.
2. composite nucleating agent according to claim 1, which is characterized in that the composite nucleating agent is by bicyclic carboxylic acid salt A and benzoic acid
Salt B composition.
3. composite nucleating agent according to claim 1 or 2, which is characterized in that R1~R10Separately it is selected from hydrogen, C1~C3 alkane
Base, hydroxyl, C1~C3 alkoxy, C2~C3 alkenyloxy group, amido, C1~C3 alkylamino radical, halogen, phenyl or alkane phenyl.
4. composite nucleating agent according to claim 1 or 2, which is characterized in that M is sodium ion or calcium ion.
5. composite nucleating agent according to claim 1 or 2, which is characterized in that bicyclic carboxylic acid salt A is two rings [2.2.1] heptane -2,
3- dicarboxylic acid disodium salt.
6. composite nucleating agent according to claim 1 or 2, which is characterized in that benzoate B is the alkali metal salt of benzoic acid.
7. composite nucleating agent according to claim 1 or 2, which is characterized in that bicyclic carboxylic acid salt A is two rings [2.2.1] heptane -2,
3- dicarboxylic acid disodium salt, benzoate B are sodium benzoate.
8. composite nucleating agent according to claim 1 or 2, which is characterized in that bicyclic carboxylic acid salt A and benzoate B weight ratio are
7:3,8:2 or 9:1.
9. the preparation method of described in any item composite nucleating agents according to claim 1~8, which is characterized in that by bicyclic carboxylic acid
Salt A and benzoate B are dispersed in water, and are sufficiently mixed the two until all dissolutions, then dry and crushing, are combined into
Core agent.
10. described in any item composite nucleating agents are improving the mechanical property of thermoplastic resin and transparent according to claim 1~8
Purposes in degree.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1906012A (en) * | 2004-01-23 | 2007-01-31 | 美利肯公司 | Process of making two-stage injection stretch blow molded polypropylene articles |
| US20080286547A1 (en) * | 2007-05-18 | 2008-11-20 | Hubbard Michael A | Polypropylene films with enhanced moisture barrier properties, process for making and composition thereof |
| CN102344609A (en) * | 2011-09-23 | 2012-02-08 | 金发科技股份有限公司 | Creep-resistant polypropylene composition and preparation method and application thereof |
| CN106633391A (en) * | 2016-11-29 | 2017-05-10 | 华东理工大学 | Inducing method of transcrystalline structure on polypropylene/glass fiber interface |
-
2019
- 2019-07-25 CN CN201910674014.4A patent/CN110343290A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1906012A (en) * | 2004-01-23 | 2007-01-31 | 美利肯公司 | Process of making two-stage injection stretch blow molded polypropylene articles |
| US20080286547A1 (en) * | 2007-05-18 | 2008-11-20 | Hubbard Michael A | Polypropylene films with enhanced moisture barrier properties, process for making and composition thereof |
| CN102344609A (en) * | 2011-09-23 | 2012-02-08 | 金发科技股份有限公司 | Creep-resistant polypropylene composition and preparation method and application thereof |
| CN106633391A (en) * | 2016-11-29 | 2017-05-10 | 华东理工大学 | Inducing method of transcrystalline structure on polypropylene/glass fiber interface |
Non-Patent Citations (2)
| Title |
|---|
| WIEBKE WUNDERLICH,ET AL.: "Nucleation of polypropylene-its challenges and solutions", 《THE INTERNATIONAL CONFERENCE ON POLYOLEFINS: FROM RESERVES TO RETAILERS--THE CHANGES CONFRONTING THE POLYOLEFINS BUSINESS》 * |
| YUE-FEI ZHANG,ET AL.: "Effects of cyclic carboxylate nucleating agents on nucleus density and crystallization behavior of isotactic polypropylene", 《J THERM ANAL CALORIM》 * |
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