CN110317364A - Nucleating agent and its preparation method and application - Google Patents
Nucleating agent and its preparation method and application Download PDFInfo
- Publication number
- CN110317364A CN110317364A CN201910674018.2A CN201910674018A CN110317364A CN 110317364 A CN110317364 A CN 110317364A CN 201910674018 A CN201910674018 A CN 201910674018A CN 110317364 A CN110317364 A CN 110317364A
- Authority
- CN
- China
- Prior art keywords
- nucleating agent
- carboxylic acid
- benzoate
- acetal
- sorbierite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
- 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
- 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
-
- 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)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of nucleating agents and its preparation method and application.Nucleating agent includes bicyclic carboxylic acid salt A, benzoate B and dibenzylidene alditols acetal C.Nucleating agent of the invention can take into account the bending modulus and transparency of thermoplastic resin.
Description
Technical field
The nucleating agent and its preparation method and application that the present invention relates to a kind of for thermoplastic resin.
Background technique
Thermoplastic resin indicates that heating can melt, and cooling can keep solid polymer material.Thermoplastic resin can be used
In storage container, medical instrument, food packaging, plastic pipe, frame component.Thermoplastic resin includes showing crystallization or half hitch
The polymer of crystalline form state, specific example include but is not limited to polyolefin, polyamide, polyurethanes, polyester etc..Thermoplasticity
The process of resin is extremely important for its performance.Under normal conditions, the thermoplastic resin 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.Some nucleation
The durability of thermoplastic resin, impact resistance etc. can be improved in agent.
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.
CN101613490B discloses a kind of polyolefin resin nucleating agent, for two acetals of polyalcohol-Silicage-polymer- bonded phase object.It is above-mentioned special
Sharp document does not fully consider bending modulus and transparency.CN1524108B discloses a kind of thermoplastic additive, packet
Include two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium and benzylidene sorbitol acetals.The additive generates low transparency simultaneously
With high nucleation efficiencies.In addition, the patent document thinks most of typical nucleating compound (such as sodium benzoate, bicyclic [2.2.1] heptan
Alkane dicarboxylic acid disodium) nucleation efficiencies of polyolefin articles can be reduced, thus it is unfavorable for the raising of its comprehensive performance.
Summary of the invention
In view of this, thermoplasticity can be taken into account it is an object of the present invention to the nucleating agent for thermoplastic resin
The bending modulus and transparency of resin.It is another object of the present invention to provide the preparation methods of above-mentioned nucleating agent.The present invention
Further object be to provide the purposes of above-mentioned nucleating agent.The present invention adopts the following technical scheme that realization above-mentioned purpose.
On the one hand, the nucleating agent for thermoplastic resin of the invention includes bicyclic carboxylic acid salt A, benzene first shown in formula (I)
Hydrochlorate B and dibenzylidene alditols acetal C:
Wherein, R1~R10Separately it is selected from hydrogen, C1~C5 alkyl, hydroxyl, C1~C5 alkoxy, C2~C6 alkene oxygen
Base, amido, C1~C5 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 is 2~3 parts by weight, and benzoate B is 5~6 parts by weight, dibenzylidene alditols acetal C
For 2.5~3.5 parts by weight.
Nucleating agent according to the present invention, it is preferable that by bicyclic carboxylic acid salt A, benzoate B and dibenzylidene alditols acetal C
Composition.
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.
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 acid disodium
Salt.
Nucleating agent according to the present invention, it is preferable that benzoate B is the alkali metal salt of benzoic acid.
Nucleating agent according to the present invention, it is preferable that dibenzylidene alditols acetal C is dibenzyl sorbitol acetal.
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 acid disodium
Salt, benzoate B are sodium benzoate, and dibenzylidene alditols acetal C is 1,3:2,4- bis- (to methylbenzilidene) sorbierite.
Nucleating agent according to the present invention, it is preferable that bicyclic carboxylic acid salt A be 2 parts by weight, benzoate B be 5 parts by weight, two
Benzylidene alditol acetals C is 3 parts by weight.
On the other hand, the preparation method of nucleating agent of the invention includes the following steps: bicyclic carboxylic acid salt A, benzoate B
It is dispersed in water, is sufficiently mixed with dibenzylidene alditols acetal C, then dry and crushing obtains nucleating agent.
In another aspect, the present invention provides use of the above-mentioned nucleating agent in the bending modulus and transparency for improving thermoplastic resin
On the way.
Three kinds of nucleating agents are combined and are used by the present invention, it has unexpectedly been found that the nucleating agent of specific proportion can improve heat simultaneously
The bending modulus and transparency of plastic resin.Preferred technical solution according to the present invention, nucleating agent of the invention can significantly change
The bending modulus of kind thermoplastic resin, while the mist degree of thermoplastic resin can be substantially reduced.
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..Nucleating agent packet for thermoplastic resin of the invention
Include bicyclic carboxylic acid salt A, benzoate B and dibenzylidene alditols acetal C.In certain embodiments, the nucleating agent is by bicyclic carboxylic
Hydrochlorate A, benzoate B and dibenzylidene alditols acetal C composition.
Bicyclic carboxylic acid salt A dosage is 2~3 parts by weight, preferably 2~2.5 parts by weight.Benzoate B is 5~6 parts by weight,
Preferably 5~5.5 parts by weight.Dibenzylidene alditols acetal C is 2.5~3.5 parts by weight, preferably 2.5~3 parts by weight.In this way
Bending modulus and transparency can be taken into account.A preferred embodiment according to the present invention, bicyclic carboxylic acid salt A are 2 parts by weight, benzene
Formates B is 5 parts by weight, and dibenzylidene alditols acetal C is 3 parts by weight.Bending modulus and transparency can be made to reach in this way
Optimum balance state.
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~C5 alkyl, hydroxyl, C1~C5 alkoxy, C2~C6
Alkenyloxy group, amido, C1~C5 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~C5 alkane phenyl.
The example of C1~C5 alkyl includes but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, just
Amyl, isopentyl, neopentyl etc.；Preferably methyl, ethyl, n-propyl or isopropyl；More preferably methyl.
The example of C1~C5 alkoxy includes but is not limited to methoxyl group, ethyoxyl, positive propoxy, isopropoxy, positive fourth oxygen
Base, isobutoxy, n-pentyloxy, isoamoxy, neopentyl oxygen etc.；Preferably methoxyl group, ethyoxyl, positive propoxy or isopropyl oxygen
Base；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~C5 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 etc.；Preferably methylamino, ethylamino-, 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.
In the present invention, dibenzylidene alditols acetal C can be dibenzyl sorbitol acetal.Dibenzylidene alditols acetal
C can be (right selected from 1,3:2,4- dibenzyl sorbitol, 1,3:2,4- bis- (to methylbenzilidene) sorbierite, 1,3:2,4- bis-
Chlorine benzal) sorbierite, 1,3:2,4- bis- (2,4- dimethyldibenzylidene) sorbierite, 1,3:2,4- bis- (to ethylbenzylidene)
(3,4- dichloros are sub- by sorbierite, 1,3:2,4- bis- (3, the 4- dimethyldibenzylidene) sorbierite for being abbreviated as 3,4-DMBS, 1,3-O-
Benzyl): 2,4-O- (3,4- dimethyl benzylidene) sorbierite, 1,3-O- (3,4- dimethyl benzylidene): 2,4-O- (3,4- dichloro
Benzal) sorbierite, 1,3-O- (3,4- difluorobenzyliden): 2,4-O- (3,4- dimethyl benzylidene) sorbierite, 1,3-O- (3,
4- dimethyl benzylidene): 2,4-O- (3,4- difluorobenzyliden) sorbierite, 1,3-O- (3,4- dichlorin benzylidene): 2,4-O- (3,
4- dimethoxybenzylidenegroup group) sorbierite, 1,3-O- (3,4- dimethoxybenzylidenegroup group): 2,4-O- (3,4- dichlorin benzylidene) sorb
Alcohol, 1,3-O- (3,4- dichlorin benzylidene): 2,4-O- (Asia 5- indanyl) sorbierite, 1,3-O- (Asia 5- indanyl): 2,4-O-
(3,4- dichlorin benzylidene) sorbierite, 1,3-O- (4- nitrobenzal): 2,4-O- (3,4- dimethyl benzylidene) sorbierite, 1,
3-O- (3,4- dimethyl benzylidene): 2,4-O- (4- nitrobenzal) sorbierite, 1,3-O- (4- nitrobenzal): 2,4-O-
(3,4- methylene dioxy benzal) sorbierite, 1,3-O- (3,4- methylene dioxy benzal): 2,4-O- (4- nitro benzal
Base) sorbierite, 1,3-O- (3,4- dichlorin benzylidene): 2,4-O- (3,4- dimethyl benzylidene) xylitol and 1,3-O- (3,4-
Dimethyl benzylidene): 2,4-O- (3,4- dichlorin benzylidene) xylitol, 1,3-O- (the fluoro- 3- methylbenzilidene of 4-): 2,4-O-
(3,4- dimethyl benzylidene) sorbierite, (the fluoro- 3- methylbenzilidene of the 4-) mountain 1,3-O- (3,4- dimethyl benzylidene): 2,4-O-
Pears alcohol, 1,3-O- (the fluoro- 3- methylbenzilidene of 4-): 2,4-O- (the fluoro- 4- methylbenzilidene of 3-) sorbierite, 1,3-O- (the fluoro- 4- of 3-
Methylbenzilidene): 2,4-O- (the fluoro- 3- methylbenzilidene of 4-) sorbierite, 1,3-O- (the fluoro- 3- methylbenzilidene of 4-): 2,4-O-
(4- chlorine benzal) sorbierite, 1,3-O- (4- chlorine benzal): 2,4-O- (the fluoro- 3- methylbenzilidene of 4-) sorbierite, 1,3-O-
(the chloro- 3- methylbenzilidene of 4-): 2,4-O- (the chloro- 4- methylbenzilidene of 3-) sorbierite, 1,3-O- (the chloro- 4- Methylbenzylidene of 3-
Base): 2,4-O- (the chloro- 3- methylbenzilidene of 4-) sorbierite, 1,3-O- (the fluoro- 3- methylbenzilidene of 4-): 2,4-O- (5 ', 6 ',
7 ', 8 '-tetrahydro -2- naphthylenes) sorbierite, 1,3-O- (5 ', 6 ', 7 ', 8 '-tetrahydro naphthylene): 2,4-O- (the fluoro- 3- methyl of 4-
Benzal) sorbierite, 1,3-O- (the chloro- 3- methylbenzilidene of 4-): 2,4-O- (5 ', 6 ', 7 ', 8 '-tetrahydro -2- naphthylene) sorb
Alcohol, 1,3-O- (5 ', 6 ', 7 ', 8 '-tetrahydro naphthylene): 2,4-O- (the chloro- 3- methylbenzilidene of 4-) sorbierite, 1,3-O- (3-
Bromo- 4- ethylbenzylidene): 2,4-O- (3,4- dimethyl benzylidene) sorbierite, 1,3-O- (the bromo- 4- isopropyl benzal of 3-):
2,4-O- (3,4- dimethyl benzylidene) sorbierite, (the 3,4- dimethyl Asia 1,3-O- (the bromo- 4- methylbenzilidene of 3-): 2,4-O-
Benzyl) sorbierite, 1,3-O- (4- chlorine benzal): 2,4-O- (the bromo- 4- isopropyl benzal of 3-) sorbierite, 1,3:2,4- be bis-
Bis- (the 3- chlorine 4- methylbenzilidene) sorbierites of (the chloro- 3- methylbenzilidene of 4-) sorbierite, 1,3:2,4-, 1,3:2,4- are bis-, and (3- is bromo-
4- isopropyl benzal) sorbierite, bis- (the bromo- 4- methylbenzilidene of the 3-) sorbierites of 1,3:2,4-, bis- (the bromo- 4- of 3- of 1,3:2,4-
Ethylbenzylidene) sorbierite, 1,3-O- (4- fluorine benzal): 2,4-O- (3,4- dimethyl benzylidene) sorbierite, 1,3-O- (3,
4- dimethyl benzylidene): 2,4-O- (4- fluorine benzal) sorbierite, 1,3-O- (3- fluorine benzal): 2,4-O- (3,4- dimethyl
Benzal) sorbierite, 1,3-O- (3,4- dimethyl benzylidene): 2,4-O- (3- fluorine benzal) sorbierite, 1,3-O- (3,4- bis-
Methylbenzilidene): 2,4-O- (4- trifluoromethyl benzal) sorbierite, 1,3-O- (4- trifluoromethyl benzal): 2,4-O- (3,
4- dimethyl benzylidene) sorbierite, 1,3-O- (4- tert-butyl benzal): 2,4-O- (3,4- dimethyl benzylidene) sorbierite,
1,3-O- (3,4- dimethyl benzylidene): 2,4-O- (4- tert-butyl benzal) sorbierite, 1,3-O- (3,4- dimethoxy benzal
Base): 2,4-O- (3,4- dimethyl benzylidene) sorbierite, 1,3-O- (3,4- dimethyl benzylidene): 2,4-O- (3,4- dimethoxy
Base benzal) sorbierite, 1,3-O- (3,4- methylene dioxy benzal): 2,4-O- (3,4- dimethyl benzylidene) sorbierite,
(4- isopropyl is sub- by 1,3-O- (3,4- dimethyl benzylidene): 2,4-O- (3,4- methylene dioxy benzal) sorbierite, 1,3-O-
Benzyl): 2,4-O- (3,4- dimethyl benzylidene) sorbierite, 1,3-O- (3,4- dimethyl benzylidene): 2,4-O- (4- isopropyl
Benzal) sorbierite, 1,3-O- (3,4- dimethyl benzylidene): 2,4-O- (2- naphthalene benzal) sorbierite, 1,3-O- (2- naphthalene
Base benzal): 2,4-O- (3,4- dimethyl benzylidene) sorbierite, 1,3:2,4- bis- (4- tert-butyl benzal) sorbierites, 1,
Bis- (the 3,4- methylene dioxy benzal) sorbierites of 3:2,4-, bis- (the fluoro- 3- methylbenzilidene of 4-) sorbierites and bis- (fluoro- 4- of 3-
Methylbenzilidene) sorbierite.Preferably, dibenzylidene alditols acetal is selected from 1,3:2,4- dibenzyl sorbitol, 1,3:2,
4- bis- (to methylbenzilidene) sorbierite, 1,3:2,4- bis- (p-chlorobenzal base) sorbierite, (2, the 4- dimethyl two of 1,3:2,4- bis-
Benzal) sorbierite, (to the ethylbenzylidene) sorbierite of 1,3:2,4- bis- and 1,3:2,4- bis- (3,4- dimethyldibenzylidene)
Sorbierite.It is highly preferred that dibenzylidene alditols acetal is selected from 1,3:2,4- bis- (to methylbenzilidene) sorbierite.It can fill in this way
Divide and takes into account bending strength and transparency.
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, and dibenzylidene alditols acetal C is 1,3:2,4- bis- (to methylbenzilidene) sorbierite.
Two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium salt is 2~3 parts by weight, and sodium benzoate is 5~6 parts by weight, 1,3:2,4- bis-
(to methylbenzilidene) sorbierite is 2.5~3.5 parts by weight.Bending modulus can be improved in this way, and reduce mist degree.According to this hair
A bright preferred embodiment, two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium salt are 2 parts by weight, and sodium benzoate is 5 weights
Part is measured, (to the methylbenzilidene) sorbierite of 1,3:2,4- bis- is 3 parts by weight.Bending modulus and mist degree can be made to reach most in this way
Good equilibrium state.
The preparation method of nucleating agent of the invention includes the following steps: bicyclic carboxylic acid salt A, benzoate B and two benzal
Base alditol acetal C is dispersed in water, and is sufficiently mixed, and then dry and crushing obtains nucleating agent.There is no especially limits for the dosage of water
System.Dry and pulverization conditions are normal condition, and which is not described herein again.
In addition, the use the present invention also provides above-mentioned nucleating agent in the bending modulus and transparency for improving thermoplastic resin
On the way.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 nucleating agent.Therefore, the use the present invention also provides above-mentioned nucleating agent in the bending modulus and transparency for improving polyolefin
On the way.
Embodiment 1
By two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium salt, sodium benzoate and 1,3:2,4- bis- (to methylbenzilidene)
Sorbierite is dispersed in water, and is sufficiently mixed, and then dry and crushing obtains nucleating agent.Specific proportion is referring to table 1.
Table 1
Comparative example 1~3
By two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium salt, sodium benzoate and 1,3:2,4- bis- (to methylbenzilidene)
Sorbierite is dispersed in water, and is sufficiently mixed, and then dry and crushing obtains nucleating agent.Specific proportion is referring to table 2.
Table 2
Experimental example
The nucleating agent of embodiment 1 and comparative example 1~3 is added in acrylic resin.On the basis of polyacrylic weight,
Nucleating agent dosage is 0.56 ‰, and antioxidant 1010 dosage is 0.5 ‰, and irgasfos 168 dosage is 0.5 ‰, and 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, see Table 3 for details.Wherein, bending modulus
It 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 | 1380 | 34.6 |
| Comparative example 1 | 1280 | 36.1 |
| Comparative example 2 | 1280 | 43.4 |
| Comparative example 3 | 1280 | 36.7 |
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 nucleating agent for thermoplastic resin, including bicyclic carboxylic acid salt A shown in formula (I), benzoate B and two benzal
Base alditol acetal C:
Wherein, R1~R10Separately it is selected from hydrogen, C1~C5 alkyl, hydroxyl, C1~C5 alkoxy, C2~C6 alkenyloxy group, amine
Base, C1~C5 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 is 2~3 parts by weight, and benzoate B is 5~6 parts by weight, and dibenzylidene alditols acetal C is 2.5
~3.5 parts by weight.
2. nucleating agent according to claim 1, which is characterized in that for the nucleating agent by bicyclic carboxylic acid salt A, benzoate B and two is sub-
Benzyl alditol acetal C composition.
3. nucleating agent according to claim 1 or 2, which is characterized in 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.
4. 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- bis-
Carboxylic acid disodium salt.
5. nucleating agent according to claim 1 or 2, which is characterized in that benzoate B is the alkali metal salt of benzoic acid.
6. nucleating agent according to claim 1 or 2, which is characterized in that dibenzylidene alditols acetal C is dibenzyl sorbitol contracting
Aldehyde.
7. 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- bis-
Carboxylic acid disodium salt, benzoate B are sodium benzoate, and dibenzylidene alditols acetal C is 1,3:2,4- bis- (to methylbenzilidene) mountain
Pears alcohol.
8. nucleating agent according to claim 1 or 2, which is characterized in that bicyclic carboxylic acid salt A is 2 parts by weight, and benzoate B is 5 weights
Part is measured, dibenzylidene alditols acetal C is 3 parts by weight.
9. the preparation method of described in any item nucleating agents according to claim 1~8, which is characterized in that by bicyclic carboxylic acid salt A,
Benzoate B and dibenzylidene alditols acetal C are dispersed in water, and are sufficiently mixed, and then dry and crushing obtains nucleating agent.
10. described in any item nucleating agents are in the bending modulus and transparency for improving thermoplastic resin according to claim 1~8
Purposes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910674018.2A CN110317364A (en) | 2019-07-25 | 2019-07-25 | Nucleating agent and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910674018.2A CN110317364A (en) | 2019-07-25 | 2019-07-25 | Nucleating agent and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110317364A true CN110317364A (en) | 2019-10-11 |
Family
ID=68124441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910674018.2A Pending CN110317364A (en) | 2019-07-25 | 2019-07-25 | Nucleating agent and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110317364A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961027A (en) * | 2020-08-18 | 2020-11-20 | 上海齐润化工有限公司 | Composition and method for preparing transparent articles under low temperature conditions |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003004554A1 (en) * | 2001-07-03 | 2003-01-16 | Milliken & Company | Clarifying agent formulations for thermoplastics exhibiting very high nucleation efficacy |
| CN1513023A (en) * | 2001-06-05 | 2004-07-14 | 美利肯公司 | Novel saturated [2,2,2] dicarboxylate salt thermoplastic nucleators and thermoplastic compositions thereof |
| US7129323B2 (en) * | 2002-06-14 | 2006-10-31 | Milliken & Company | Bimolecular nucleation methods for thermoplastics |
| CN1894322A (en) * | 2003-11-07 | 2007-01-10 | 美利肯公司 | Concentrates of saturated bicyclic dicarboxylate salts as polymer nucleation additives and methods of nucleating thermoplastics |
| CN101395129A (en) * | 2006-03-03 | 2009-03-25 | 美利肯公司 | Metal carboxylate salt nucleating or clarifying agent compounds and related polymer compositions and methods |
| KR20100027877A (en) * | 2008-09-03 | 2010-03-11 | 삼성토탈 주식회사 | Polypropylene composition for thin wall injection molding |
| CN106397988A (en) * | 2015-07-30 | 2017-02-15 | Sabic环球技术有限责任公司 | Polypropylene composition |
-
2019
- 2019-07-25 CN CN201910674018.2A patent/CN110317364A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513023A (en) * | 2001-06-05 | 2004-07-14 | 美利肯公司 | Novel saturated [2,2,2] dicarboxylate salt thermoplastic nucleators and thermoplastic compositions thereof |
| WO2003004554A1 (en) * | 2001-07-03 | 2003-01-16 | Milliken & Company | Clarifying agent formulations for thermoplastics exhibiting very high nucleation efficacy |
| CN1524108A (en) * | 2001-07-03 | 2004-08-25 | Clarifying agent formulations for thermoplastics exhibiting very high nucleation efficacy | |
| US7129323B2 (en) * | 2002-06-14 | 2006-10-31 | Milliken & Company | Bimolecular nucleation methods for thermoplastics |
| CN1894322A (en) * | 2003-11-07 | 2007-01-10 | 美利肯公司 | Concentrates of saturated bicyclic dicarboxylate salts as polymer nucleation additives and methods of nucleating thermoplastics |
| CN101395129A (en) * | 2006-03-03 | 2009-03-25 | 美利肯公司 | Metal carboxylate salt nucleating or clarifying agent compounds and related polymer compositions and methods |
| KR20100027877A (en) * | 2008-09-03 | 2010-03-11 | 삼성토탈 주식회사 | Polypropylene composition for thin wall injection molding |
| CN106397988A (en) * | 2015-07-30 | 2017-02-15 | Sabic环球技术有限责任公司 | Polypropylene composition |
Non-Patent Citations (4)
| Title |
|---|
| SHINTA NAGASAWA,ET AL.: "Crystallisation of polypropylene containing nucleators", 《POLYMER》 * |
| WENTAO HAO AND WEN YANG: "Comparison Between Crystalline Morphology of Isotactic Polypropylene with Di-p-methylbenzylidene Sorbitol and Sodium Benzoate", 《ASIAN JOURNAL OF CHEMISTRY》 * |
| 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》 * |
| 秦立福等: "复合成核剂对PBT结晶行为的影响", 《塑料工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961027A (en) * | 2020-08-18 | 2020-11-20 | 上海齐润化工有限公司 | Composition and method for preparing transparent articles under low temperature conditions |
| CN111961027B (en) * | 2020-08-18 | 2023-11-17 | 上海齐润新材料有限公司 | Composition and method for preparing transparent articles at low temperature |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110317364A (en) | Nucleating agent and its preparation method and application | |
| CN103030886A (en) | Transparent polypropylene and preparing method thereof | |
| CN101265347B (en) | Polypropylene transparent nucleater | |
| JP2008542522A (en) | Flame retardant composition exhibiting excellent thermal stability and flame retardancy and use thereof | |
| US6642290B1 (en) | Highly nucleated syndiotactic polypropylene | |
| ES2686127T3 (en) | Composition of quinone methyl amines derivatives and for the control and inhibition of polymerization of monomers, and process of preparation and use thereof | |
| CN106478990A (en) | A kind of novel melting one-step method prepares hydroxy fatty acid calcium zinc PVC stabilizer | |
| CN103665383A (en) | Oligomeric phosphate compound and preparation method | |
| CN107540559A (en) | A kind of antioxidant 4,4 ' is double（α, α dimethyl benzyl）The preparation method of diphenylamines | |
| CN110305414A (en) | Polyolefin composition and preparation method thereof | |
| CN105647016B (en) | Preparation method of polypropylene organic composite nucleating agent | |
| ES2964559T3 (en) | Procedure for the production of pentaerythritol with an increased yield of dipentaerythritol | |
| US6703434B2 (en) | Methods of producing highly nucleated syndiotactic polypropylene | |
| CN103936560B (en) | A kind of 3, the preparation method of 3 '-dimethyl-4,4 '-'-biphenyl diphenol | |
| CN105367924B (en) | A kind of granulating plastic additive and the preparation method and application thereof | |
| CN110343290A (en) | Composite nucleating agent and its preparation method and application | |
| JP6848856B2 (en) | Ethylene-vinyl ester copolymer saponified composition and method for producing the same | |
| US20040010107A1 (en) | Highly nucleated syndiotactic polypropylene | |
| EP2523999A2 (en) | Nucleating agents for polyolefins based on metal salts | |
| CN104163984A (en) | Polyolefin resin composition and preparation method thereof | |
| CN110343328A (en) | Thermoplastic resin composition and preparation method thereof | |
| CN104262777A (en) | Flame-retardant polypropylene of nano allophane synergistic intumescent flame retardant and preparation method of flame-retardant polypropylene | |
| CN104098827A (en) | High-strength PE water supply pipe material and preparation method thereof | |
| CN112898681A (en) | Polypropylene composition, process for producing the same and use thereof | |
| JP2016113466A (en) | Vinylidene fluoride resin composition, molded article and manufacturing method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191011 |
|
| RJ01 | Rejection of invention patent application after publication |