CN105754142B - A kind of reinforcement nucleating agent composition containing hydrotalcite - Google Patents
A kind of reinforcement nucleating agent composition containing hydrotalcite Download PDFInfo
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- CN105754142B CN105754142B CN201610111971.2A CN201610111971A CN105754142B CN 105754142 B CN105754142 B CN 105754142B CN 201610111971 A CN201610111971 A CN 201610111971A CN 105754142 B CN105754142 B CN 105754142B
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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Abstract
The present invention relates to a kind of reinforcement nucleating agent composition containing hydrotalcite, while it is related to the thermoplastic containing the nucleating agent compositions, more particularly to the nylon containing the nucleating agent compositions.The nucleating agent compositions contain two [4 p t butylbenzoic acid] hydroxy Als and hydrotalcite, and the weight ratio of the two is 5:1~1:5.The nucleating agent compositions have better nucleating effect, and stretching, the bending strength height of gained nylon products, and impact strength loss is small, heat-resist etc..The nucleating agent of the present invention improves nylon process demolding performace, shorten injection molding cycle, so as to improve production efficiency, on the other hand, the dimensional stability of product is improved, reduces shrinking percentage, while further improves the mechanical performance of product, product transparency is improved, improves heat resisting temperature.
Description
Technical field
The present invention relates to nucleating agent fields, and in particular to a kind of reinforcement nucleating agent composition containing hydrotalcite relates to simultaneously
And the thermoplastic containing the nucleating agent compositions, more particularly to the nylon containing the nucleating agent compositions.
Technical background
Thermoplastic refers to there is the plastics heated and softened as flowing, hardening by cooling characteristic, can be by injecting, squeezing
Go out and be blow-moulded into that there is injection-molded item for various purposes, such as daily life product, medical apparatus, electric appliance, automobile and pipe
Material pipeline etc..Thermoplastic polymer according to the present invention includes but not limited to polyolefin (such as polyethylene, polypropylene, poly- fourth
Alkene and any combination thereof), polyamide (such as nylon), polyurethanes, polyester (such as polyethylene terephthalate) and
Its analog.
Polyamide is commonly called as nylon, and nylon is one of most important five big general engineering plastics, is in great demand.In nylon
Principal item is nylon 6 (PA6) and nylon66 fiber (PA66), they are numerous by squeezing out the obtained nylon product species of Shooting Technique
It is more, such as enhance nylon, high-impact (toughening) nylon, electroconductive nylon, fire-retardant nylon, nylon and other polymers blend and alloy
Etc..These nylon injection-molding products possess many spies such as higher mechanical strength, heat-resisting, coefficient of friction is low, self lubricity, oil resistant
Point is widely used in the fields such as automobile, electric, domestic consumer product, household electrical appliance.In the production of many nylon injection-molding products
In the process, the problems such as generally existing crystalline rate is relatively slow, the demoulding is difficult, poor dimensional stability, for this purpose, by adding nucleating agent pair
Nylon is modified, and improves the crystalline rate of nylon, and nylon product had both shortened molding cycle, its demolding performace, dimensionally stable
Property and mechanical property are also effectively improved.The application field of nucleater modified nylon is extensive, they can be used as automobile into collection
Tracheae, engine bonnet, gear, band, electronic connector, electric power connector etc..However, existing commercial nylon nucleating agent
Species is seldom, and the nucleating agent with excellent application effect is then less.
At present, the preferable nylon nucleating agent of performance has the nucleation that German Brueggemann Bruggolen is released in industrial production
The nucleating agent CAV102 that agent P22 and German Clariant Clariant are released.It is usually of interest at present special in thermoplastic
It is not that addition nucleating agent correlated performance is mainly following aspect in nylon：1st, fast polymer crystallization speed and/or highly crystalline temperature
Degree, polymer melt are cooled and solidified in crystallization process, and macromolecular long-chain needs longer relaxation by the crystalline state of disorder to order
Time, crystalline rate and crystallization temperature are all low, and can form larger spherocrystal, and there are apparent interfaces between spherocrystal to cause not
With internal stress, be also easy to produce crackle when by external impacts and rupture, and in the cooling procedure of polymer melt preparaton plus
After entering nucleating agent, the nucleating point used in crystal growth is provided using immunomodulator compounds are nucleated so that crystallization rate is accelerated, so that
It obtains and is crystallized at relatively high temperatures, and high polymer peak crystallization temperature represents high nucleation effect；It is finally embodied in
From the point of view of manufacturing on component, high nucleation effect generally means that fast process-cycle and more preferably physical property such as hardness, bullet
Property modulus, tensile strength, impact balance etc., in general, the rigidity of thermoplastic is characterized by bending modulus, toughness by
Impact strength characterizes；2nd, the high grade of transparency：Need thermoplastic articles itself that there is good transparency at present, in the plastic
Homodisperse nucleating agent becomes smaller, and crystal becomes subtle, and the crystal of miniaturization reduces on crystalline portion and amorphous fraction interface
Scattering, when crystalline size be less than 1 micron when, the transparency sharply increases.
In addition, in the process of thermoplastic particularly nylon, there is following puzzlement toward contact：1st, release property
Energy：Most nylon not easy mold releases, and mobility is not strong in injection moulding process currently on the market, puzzlement is brought to manufacture, because
Using addition releasing agent in this processing of overwhelming majority at present, however belong to environmental requirement containing polycyclic fragrant cyanogen in releasing agent
In the ingredient that strictly limits, in order to ensure safety, meet the requirement of environmental protection, most direct method is exactly that raw material easily take off in itself
Mould need not use releasing agent.
In the prior art, thermoplastic nucleator is divided into organic and two kinds inorganic, and organic nucleating agent mainly has phosphoric acid gold
Belong to salt, carboxylic metallic salt and glucitol derivative and polymer type, organic nucleating agent usually has good with fluoropolymer resin
Compatibility, can significantly improve product the transparency and show gloss.Aromatic carboxylic acid's metal salt is crystallized using beta crystal-type nucleater
Mechanism can significantly improve the toughness of fluoropolymer resin, but property compatible is poor.Inorganic nucleating agent mainly have talcum powder,
Titanium dioxide, nano silicon dioxide etc., this kind of nucleating agent abundance are inexpensive, but have to the transparency and lustrous surface of product
Certain to influence, using effect is poor, and application range is limited to.Hydrotalcite uses application in high molecular polymer field as auxiliary agent
Extensively, particularly as acid absorbent and nucleating agent synergist, on its being applied in combination with other nucleating agents, CN102558683A
It discloses a kind of polypropylene beta crystal form nucleating agent composition, by the carboxylic metallic salt and adjuvant of beta crystal-type nucleater tetrahydrophthalic anhydride
Calcium carbonate, hydrotalcite or talcum powder mix, and in addition, have no the related report that it is applied in combination to other nucleating agents
Road.
The research for being configured to composite nucleating agent on two or more nucleating agents at present is increasingly becoming hot spot.And by it is a variety of into
Core agent is entrained in the region for being used together and prediction being very difficult in chemical field, unless by attempting, testing and complete relatively large
Otherwise the work of amount can not usually know which kind of substance is effective.
It needs to provide a kind of nucleating agent for thermoplastic, particularly nylon at present, fast polymer can be had both
While crystallization rate and/or high crystallization temperature, the high grade of transparency, also improve to some extent on demolding performace and thermal stability.This
Patent application people explores by prolonged, develops a kind of nucleating agent compositions, the composition compared to its independent component and
Speech, has greatly improved in above-mentioned performance.
The content of the invention
It is an object of the present invention to provide a kind of reinforcement nucleating agent composition containing hydrotalcite, the nucleating agent combination
Object further improved simultaneously while generate high nucleation efficiencies in target thermoplastic product product demolding performace and heat it is steady
Qualitative energy；The high nucleation efficiencies show as fast polymer crystallization speed and/or high crystallization temperature, so as to finally so that product
Impact strength, bending modulus and heat distortion temperature be all significantly improved.
The second object of the present invention is to provide the application by above-mentioned nucleating agent compositions in thermoplastic.
The third object of the present invention is to provide the application in nylon by above-mentioned nucleating agent compositions.
To achieve these goals, the present invention provides a kind of reinforcement nucleating agent composition containing hydrotalcite, it is described into
Core agent composition contains two-[4- p t butylbenzoic acids] hydroxy Al and hydrotalcite, and the weight ratio of the two is 5:1~1:5.
Preferably, two-[4- p t butylbenzoic acids] hydroxy Al and the weight ratio of hydrotalcite are 3:1~1:3；Most preferably,
The weight ratio of the two is 1:1.
Preferably, the hydrotalcite is magnalium hydrotalcite, and general formula composition is Mg1-XAlX(OH)2(An-)x/n·mH2O, formula
Middle x=0.2~0.33, An-Selected from CO3 2-、NO3 -Or Cl-, n is 1 or 2, m=1~10；It is highly preferred that the hydrotalcite for it is cloudy from
Son is CO3 2-Magnalium hydrotalcite, average grain diameter be 0.1~2.0 micron；More preferably 0.1~0.4 micron.
The present invention further provides the applications by above-mentioned nucleating agent compositions in thermoplastic.
The present invention further provides the applications by above-mentioned nucleating agent compositions in nylon.
It is used to improve impact strength, the bending die of nylon products simultaneously the present invention provides above-mentioned nucleating agent compositions
Amount, release property, thermal stability.
The present invention also provides a kind of nylon material, nylon material includes above-mentioned nucleating agent compositions and nylon, wherein
The weight of nucleating agent compositions accounts for the 0.01-2.00% of nylon weight；Preferably 0.05-1.00%；Further preferably 0.05-
0.50%；Particularly preferably 0.05-0.15%.
" thermoplastic " according to the present invention can melt when referring to exposed to enough heats, but carry out cold enough
It will keep solid-state when but but if mould or the like do not utilized not keep former shaped polymer material.Specifically,
The term also can only include the polymer that following wide scope defines：After melt body formation, crystallization can also be shown by cooling
Or the polymer of hypocrystalline form.Thermoplastic polymer according to the present invention include but not limited to polyolefin (such as polyethylene,
Polypropylene, polybutene and any combination thereof), polyamide (such as nylon), polyurethanes, polyester (such as poly- terephthaldehyde
Sour second diester) and the like.
" nylon " according to the present invention includes nylon 6 (PA6) and nylon66 fiber (PA66).
Unless otherwise indicated, " % " in the application refers to weight percent.
When the above-mentioned nucleating agent compositions of the present invention are mixed with nylon, other materials can be added in improve nylon products
Other performances.
It is rigid, tough in raising thermoplastic articles that nucleating agent compositions provided by the present invention compensate for single nucleating agent
In the case that the performances such as property, release property, thermal stability are bad, the function of giving full play to various nucleating agents in nucleating agent compositions is excellent
Gesture so that final products can have both above-mentioned multiple performance.
The nucleating agent compositions of the present invention can significantly improve the processing heat stability of product.By institute in plastic processes
Auxiliary agent or plastics have acid substance decomposition or releasing in itself, be easy to cause plastics discoloration, influence to process thermostabilization
Property, nucleating agent compositions of the invention inhale the acid thermostabilization that can ensure its process by the hydrotalcite added in because it has
Property.
The nucleating agent of the present invention is compared with the art representative nylon nucleating agent P22 and CAV102, this hair
Bright nucleating agent compositions have better nucleating effect, and stretching, the bending strength height of gained nylon, impact strength loss
It is small, it is heat-resist etc..The nucleating agent of the present invention improves nylon process demolding performace, shortens injection molding cycle, from
And production efficiency is improved, on the other hand, the dimensional stability of product is improved, reduces shrinking percentage, while further improves production
The mechanical performance of product improves product transparency, improves heat resisting temperature.
Specific embodiment
The present invention can be furtherd elucidate by following embodiment, but simply the preferred embodiment of the present invention provided herein,
The scope of the present invention is not limited thereto.
First, embodiment is prepared：
Raw material sources：Two-[4- p t butylbenzoic acids] hydroxy Al and hydrotalcite are commercial product.
Nylon is that (product type is PA6：M2800).
1st, the preparation of nucleating agent compositions of the present invention
Embodiment 1：
Two-[4- p t butylbenzoic acids] hydroxy Al 8.3g, hydrotalcite 1.7g are accurately weighed respectively, then in blender
Even mixing obtains nucleating agent 1 of the present invention.
Embodiment 2：
Two-[4- p t butylbenzoic acids] hydroxy Al 1.7g, hydrotalcite 8.3g are accurately weighed respectively, then in blender
Even mixing obtains nucleating agent 2 of the present invention.
Embodiment 3：
Two-[4- p t butylbenzoic acids] hydroxy Al 7.5g, hydrotalcite 2.5g are accurately weighed respectively, then in blender
Even mixing obtains nucleating agent 3 of the present invention.
Embodiment 4：
Two-[4- p t butylbenzoic acids] hydroxy Al 2.5g, hydrotalcite 7.5g are accurately weighed respectively, then in blender
Even mixing obtains nucleating agent 4 of the present invention.
Embodiment 5：
Two-[4- p t butylbenzoic acids] hydroxy Al 5g, hydrotalcite 5g are accurately weighed respectively, are then uniformly mixed in blender
It closes, obtains nucleating agent 5 of the present invention.
2nd, Application Example
Application of the nucleating agent of the present invention in PA6
Nucleating agent 1 prepared by embodiment 1 is made according to the 0.15% additive amount double screw extruder extrusion of PA6 mass
Grain, dry, 250 DEG C of processing temperature, obtained nylon particles 1.
Based on identical method, nylon particles 2-5 is made in the nucleating agent 2-5 for respectively preparing above-described embodiment 2-5 respectively.
Except the addition of nucleating agent is in addition to 0.05%, based on identical method, respectively by above-described embodiment 1-5 prepare into
Nylon particles 6-10 is made in core agent 1-5 respectively.
Similarly, the condition prepared according to nylon particles 1 does not add the nylon particles control sample that nucleating agent prepares blank
Product.
Similarly, the condition prepared according to nylon particles 1, adds common nylon nucleating agent P22 currently on the market respectively
And nylon particles P22 and nylon particles CAV102 is made in CAV102, addition 0.15%.
2nd, performance test embodiment
1st, crystallization temperature and stripping result are tested
It is tested for the crystallization temperature for the nylon (PA6) for adding nucleating agent compositions of the present invention using DSC, it is specific as follows：
260 DEG C are warming up to the heating rate of 10 DEG C/min under a nitrogen atmosphere, then constant temperature 3min is cooled to 25 with 10 DEG C/min
DEG C, 260 DEG C then are warming up to 10 DEG C/min again, records temperature lowering curve and second of heating curve.
Demolding performace is divided into following 4 ranks according to the required time is demoulded completely：
(1) it is poor --- sticking to mould；
(2) in --- human assistance demoulds；
(3) it is good --- energy automatic demoulding substantially wants human assistance once in a while；
(4) it is excellent --- the fully automated demoulding.
The following table 1 shows that the composition of the present invention is applied to the corresponding crystallization temperature of its in nylon with different dosage and ratio
Degree and stripping result.
Table 1 two-[4- p t butylbenzoic acids] hydroxy Al and hydrotalcite composition imitate the demoulding of PA6 crystallization temperatures and product
Fruit
As it can be seen from table 1 when two-[4- p t butylbenzoic acids] hydroxy Al and hydrotalcite Application of composite, the crystallization temperature of PA6
It spends apparently higher than each component during independent addition, the two plays apparent synergistic effect during the heterogeneous nucleation of PA6,
Demolding performace is also improved simultaneously；Further, the results showed that, when the ratio of the two is 1:When 1, best results.
2nd, mist degree test, bending modulus test, impact strength test, heat distortion temperature test are carried out
By nylon particles 1-10, the nylon particles control sample and currently on the market prepared by above application embodiment
Nylon nucleating agent P22 and CAV102 be molded into standard batten respectively, injection temperature is 270 DEG C.Test it as follows
Mist degree, bending modulus, impact strength and heat distortion temperature.
Mist degree：It is tested according to the method in ASTMD1003-07 testing standards；
The test of nucleater modified nylon is by GB 2918-1998 (plastic sample status adjustment and the standard environment of experiment)
Regulation, in (23 ± 2) DEG C, relative humidity (RH) carries out under conditions of being (50 ± 5) %, sample status adjustment time 48h.Physics
Performance test is carried out respectively by national standard：Izod notched impact strength performs standard GB/T1843-1996, and bending modulus is held
The quasi- GB/T9341-2000 of rower, heat distortion temperature perform standard GB/T 1634-2004.Test result is listed in the table below 2：
The multiple performance of the 2 nucleater modified PA6 (M2800) of the present invention of table
From Table 2, it can be seen that compared with blank control and conventional in the market P22 and CAV102, it is using the present invention
The nylon particles 1-10 that nucleating agent 1-10 is prepared is more excellent in mist degree, bending modulus and heat distortion temperature positive effect, liquidates
The loss of hit intensity is slightly excellent；The improvement of the bending modulus greatly increases the rigidity of product.With regard to nylon particles 1-10 in itself
For, wherein two in nucleating agent-ratio 1 of [4- p t butylbenzoic acids] hydroxy Al and hydrotalcite:1 nylon particles 5 and nylon
Each performance of particle 10 shows optimal again.
A kind of reinforcement nucleating agent composition containing hydrotalcite of the present invention is described by specific example,
Those skilled in the art can use for reference present invention, and the links such as appropriate feed change, process conditions realize corresponding other mesh
, correlation changes all without departing from present disclosure, and all similar substitutions and modifications are come for those skilled in the art
Say it is it will be apparent that being considered as being included within the scope of the present invention.
Claims (4)
1. a kind of application of reinforcement nucleating agent composition of the reinforcement nucleating agent composition containing hydrotalcite in nylon, feature
It is, the nucleating agent compositions contain two-[4- p t butylbenzoic acids] hydroxy Al and hydrotalcite, and the weight ratio of the two is 1:1.
2. application according to claim 1, which is characterized in that hydrotalcite is that anion is CO3 2-Magnalium hydrotalcite,
Average grain diameter is 0.1~2.0 micron.
3. application according to claim 2, which is characterized in that the hydrotalcite is that anion is CO3 2-Magnalium neatly
Stone, average grain diameter are 0.1~0.4 micron.
4. application according to claim 1, which is characterized in that the nucleating agent compositions are used to improve nylon products simultaneously
Impact strength, bending modulus, release property, the transparency and inhale acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610111971.2A CN105754142B (en) | 2016-02-29 | 2016-02-29 | A kind of reinforcement nucleating agent composition containing hydrotalcite |
| PCT/CN2017/074246 WO2017148302A1 (en) | 2016-02-29 | 2017-02-21 | Rigidity-enhancing nucleating agent composition containing hydrotalcite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610111971.2A CN105754142B (en) | 2016-02-29 | 2016-02-29 | A kind of reinforcement nucleating agent composition containing hydrotalcite |
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| CN105754142B true CN105754142B (en) | 2018-06-01 |
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| CN105754142B (en) * | 2016-02-29 | 2018-06-01 | 呈和科技股份有限公司 | A kind of reinforcement nucleating agent composition containing hydrotalcite |
| CN112430389B (en) * | 2020-11-17 | 2022-04-01 | 美瑞新材料股份有限公司 | Reinforced and toughened TPU material and preparation method thereof |
| CN113004611A (en) * | 2021-02-26 | 2021-06-22 | 张家港优全汽配有限公司 | Preparation method of low-VOC (volatile organic compound) automotive interior material |
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| CN101805941B (en) * | 2010-04-13 | 2012-12-05 | 东华大学 | Preparation method of polylactic acid fiber with high melting point |
| CN102558683B (en) * | 2011-12-31 | 2014-01-22 | 广州呈和科技有限公司 | Polypropylene beta crystal form nucleating agent composition and application thereof |
| CN105754142B (en) * | 2016-02-29 | 2018-06-01 | 呈和科技股份有限公司 | A kind of reinforcement nucleating agent composition containing hydrotalcite |
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2016
- 2016-02-29 CN CN201610111971.2A patent/CN105754142B/en active Active
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| CN1922260A (en) * | 2004-02-24 | 2007-02-28 | 株式会社艾迪科 | Flame retardant composition with enhanced fluidity, flame retardant resin composition and molding thereof |
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| CN105754142A (en) | 2016-07-13 |
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Address after: 510540 Guangzhou Province, Baiyun District, North Road, No. 1633, Guangzhou private science and Technology Park Road, No. 2, No. Applicant after: GCH TECHNOLOGY Co.,Ltd. Address before: 510540 Guangzhou Province, Baiyun District, North Road, No. 1633, Guangzhou private science and Technology Park Road, No. 2, No. Applicant before: Guangdong Chenghe Science and Technology Co.,Ltd. Address after: 510540 Guangzhou Province, Baiyun District, North Road, No. 1633, Guangzhou private science and Technology Park Road, No. 2, No. Applicant after: Guangdong Chenghe Science and Technology Co.,Ltd. Address before: 510540, No. 2, strong road, Guangzhou hi tech Industrial Development Zone, 1633 North Road, Baiyun District, Guangdong, Guangzhou Applicant before: GCH Technology Co.,Ltd. |
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