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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- Prior art keywords
- nucleating agent
- composite nucleating
- benzoate
- carboxylic acid
- acid salt
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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
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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
- C08K5/09—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
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- 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
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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Application publication date: 20191018 |