CN106905614A - A kind of high rigidity polypropene composition - Google Patents
A kind of high rigidity polypropene composition Download PDFInfo
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- CN106905614A CN106905614A CN201610574025.1A CN201610574025A CN106905614A CN 106905614 A CN106905614 A CN 106905614A CN 201610574025 A CN201610574025 A CN 201610574025A CN 106905614 A CN106905614 A CN 106905614A
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic 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
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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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
- 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
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention belongs to field of polypropylene modification, and in particular to a kind of high rigidity polypropene composition.Polypropene composition of the present invention is made up of the raw material of following parts by weight：Acrylic resin 100；Heat stabilizer 0.08 ~ 1.8；Metallic stearates 0.02 ~ 0.4；Inorganic filler 0.05 ~ 0.25；Organic nucleator 0.05 ~ 0.15.Polypropylene resin composite of the invention is prepared by the way that granulation is blended using acrylic resin, heat stabilizer, Metallic stearates, inorganic filler and a small amount of nucleator, with high rigidity, heat-resisting and low cost advantage high, preparation is simple, and the polypropylene resin composite can be applied to the fields such as automobile, household electrical appliances and household.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of high rigidity polypropene composition.
Background technology
Acrylic resin is due to excellent rigidity and heat resistance, and post-modification means are abundant, therefore just progressively
Some engineering plastics are substituted, is widely used in the fields such as automobile, household electrical appliances and household.Especially impact copolymer polypropylene resin, by
In the progress of production technology and catalyst technology, the more excellent combination property of product is imparted.But because crushing-resistant copolymerization is poly-
The production of propylene has larger technical difficulty, especially at aspects such as product rigidity, toughness and mobility, can't expire completely
The sufficient demand in some fields, therefore also need to carry out post-modification on the basis of the existing trade mark of impact copolymer polypropylene, that is, lead to
Addition nucleator, elastomer, inorganic filler, degradation agent etc. is crossed to realize high rigidity, high tenacity and high fluidity of material etc..
The rigid raising of polypropylene material is generally obtained by way of adding nucleator or inorganic filler.
With the increase of the inorganic filler such as addition such as calcium carbonate, talcum powder, mica, diatomite, acrylic resin it is curved
Qu Qiangdu and the modulus of elasticity in static bending are stepped up, but can reduce polyacrylic elongation and impact strength simultaneously, influence polypropylene
Color and luster and shrinkage factor of product etc., and the addition of high amount of inorganic filler can improve the density of material, constrain the light weight of product
Change, be especially restricted in automobile-used field.
In recent years, application of the nucleator in polypropylene is progressively increased, and many petrochemical plants are made production acrylic resin
Add nucleator, not only the addition of nucleator to have no adverse effects polyacrylic color and luster during grain, and poly- third can be improved
The heat resistance and glossiness of olefine resin.The amount of being usually added into is 0.05% ~ 0.5%, although addition is small, but because nucleator price is high
It is expensive（According to product quality and technical merit, price is generally tens of thousands of to 500,000 ten）, acrylic resin ton cost can be increased
Hundreds of yuan.
Document（The synthesis of metal carboxylate nucleator and its rigidity enhanced, modified polypropylene petrochemical technology and application, 2007,
Vol.25, No.4）0.3 ~ 0.5% metal carboxylate nucleator of addition is to improving the crystallinity of material in pure HOPP resin
Energy, hot property and the modulus of elasticity in static bending.
Patents CN101190988A discloses a kind of high glaze heat-resistance polypropylene resin combination, and homopolymerization is contained in formula
Polypropylene, 0.04 ~ 0.1% nucleator, 0.04 ~ 0.08% lubricant, 0.06 ~ 0.12% antioxidant etc., without inorganic filler.
Prior art improves rigidity and heat resistance of acrylic resin etc. by adding a large amount of nucleators, relatively costly.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of high rigidity polypropene composition, acrylic resin combination
Thing be granulation when using compounding by way of add a small amount of nucleator and a small amount of inorganic filler, the acrylic resin group being made
Compound has high rigidity, heat-resisting and low cost advantage high.
Polypropene composition of the present invention, is made up of the raw material of following parts by weight：
Acrylic resin 100
Heat stabilizer 0.08 ~ 1.8
Metallic stearates 0.02 ~ 0.4
Inorganic filler 0.05 ~ 0.25
Organic nucleator 0.05 ~ 0.15.
Described acrylic resin is commercially available impact copolymer polypropylene resin-oatmeal.
Described impact copolymer polypropylene resin is any one in propylene and ethene, 1- butylene, 1- hexenes or 1- octenes
The copolymer of alpha-olefin, wherein alpha-olefin content are 2 ~ 16mol%, the melt mass flow rate of impact copolymer polypropylene resin
（MFR, 2.16kg, 230 DEG C）It is 1 ~ 20g/10min, Mw/Mn is 4 ~ 8.
The preferred impact copolymer polypropylene QP73N powder of described impact copolymer polypropylene resin-oatmeal and impact copolymer polypropylene
QP83N powder.Impact copolymer polypropylene QP73N powder and impact copolymer polypropylene QP83N powder, by Sinopec, asphalt in Shenli Refinery gives birth to
Produce, HOPP X30S powder is produced by Dushanzi petro-chemical corporation.
Described heat stabilizer be Hinered phenols antioxidant or/and phosphite ester kind antioxidant, Hinered phenols antioxidant with
The weight ratio of phosphite ester kind antioxidant is 1:0.1~10.
Described Hinered phenols antioxidant is：Four [methyl-β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic ester] season penta
Four alcohol esters, β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester of propionic acid, 1,3,5- trimethyls -2,4,6- three（3,5-
Di-tert-butyl-4-hydroxyl benzyl）Benzene or 2,2- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate].
Described phosphite ester kind antioxidant is：Three（2,4- di-tert-butyl-phenyls）It is phosphite ester, double（2,4- di-t-butyls
Phenol）Pentaerythritol diphosphites or diphosphorous acid pentaerythrite distearyl alcohol ester.
Described Metallic stearates are zinc stearate or calcium stearate, and preferably addition is 0.05 ~ 0.3 part, stearic acid
The acidic catalyst residue in acid-acceptor and acrylic resin that functions as of slaine reacts generation stearate, together
When have lubrication concurrently.
Described inorganic filler is calcium carbonate, talcum powder, diatomite or mica, preferably calcium carbonate and talcum powder, most preferably
Talcum powder, preferably addition are 0.1 ~ 0.2 part, and inorganic filler particle size is 0.01 ~ 50 μm, preferably 0.1 ~ 10 μm.
Described organic nucleator is phosphate metal salt nucleator, and preferably addition is 0.1 ~ 0.15 part.
The described preferred nucleator HPN-68L of phosphate metal salt nucleator, nucleant agent N A11 or nucleant agent N A21.Nucleation
The chemical name of agent NA11 is di-2-ethylhexylphosphine oxide（2,4- di-tert-butyl-phenyls）Phosphoric acid ester sodium, the chemical name of nucleant agent N A21 is
Di-2-ethylhexylphosphine oxide（2,4- di-tert-butyl-phenyls）Phosphate hydroxyl aluminium salt.Nucleator HPN-68L is produced for Milliken chemical company, into
Core agent NA11 or nucleant agent N A21 is produced for Ciba Specialty Chemicals.
Beneficial effects of the present invention are as follows：
The present invention adds a small amount of nucleator and a small amount of inorganic filler when acrylic resin powder is granulated by the way of compounding, can
Meet or exceed the bending modulus and heat distortion temperature of the acrylic resin prepared by a large amount of nucleators of addition, the polypropylene being made
Resin combination not only has high rigidity, heat-resisting, low cost advantage high, 100 ~ 300 yuan of per ton cost reduction, and will not carry
The density of material high, it is ensured that the lightweight of product.
Specific embodiment
The present invention is described further with reference to embodiments.
The melt mass flow rate MFR being related in the present embodiment, is carried out according to GB/T 3682-2000, and experiment condition is equal
It is load 2.16kg, 230 DEG C of temperature.Impact copolymer polypropylene QP73N powder and impact copolymer polypropylene QP83N powder, by Chinese stone
Change asphalt in Shenli Refinery's production, HOPP X30S powder is produced by Dushanzi petro-chemical corporation.
Embodiment 1
Impact copolymer polypropylene QP73N powder（MFR=13.2g/10min, ethylene contents 8.6mol/%, Mw/Mn are 5.8） 1000g
Four [methyl-β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic ester] pentaerythritol ester 0.5g
Zinc stearate 2g
Talcum powder（5 μm of grain fineness） 2g
Nucleator（HPN-68L） 0.5g
Embodiment 2
Impact copolymer polypropylene QP73N powder（MFR=13.2g/10min, ethylene contents 8.6mol/%, Mw/Mn are 5.8） 1000g
Four [methyl-β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic ester] pentaerythritol ester 0.5g
Three（2,4- di-tert-butyl-phenyls）Phosphite ester 0.5g
Zinc stearate 3g
Talcum powder（2 μm of grain fineness） 0.5g
Nucleator（HPN-68L） 0.5g
Embodiment 3
Impact copolymer polypropylene QP73N powder（MFR=13.2g/10min, ethylene contents 8.6mol/%, Mw/Mn are 5.8） 1000g
β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester 1g of propionic acid
Diphosphorous acid pentaerythrite distearyl alcohol ester 1g
Calcium stearate 2g
Calcium carbonate（4 μm of grain fineness） 2g
Nucleator（NA21） 0.06g
Comparative example 1
Impact copolymer polypropylene QP73N powder（MFR=13.2g/10min, ethylene contents 8.6mol/%, Mw/Mn are 5.8） 1000g
Four [methyl-β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic ester] pentaerythritol ester 0.5g
Three（2,4- di-tert-butyl-phenyls）Phosphite ester 0.5g
Zinc stearate 0.5g
Nucleator（HPN-68L） 0.6g
Comparative example 2
HOPP X30S powder（MFR 11g/10min, Mw/Mn are 4.6） 1000g
β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester 1g of propionic acid
It is double（2,4- DI-tert-butylphenol compounds）Pentaerythritol diphosphites 1g
Zinc stearate 2g
Nucleator（NA21） 1g
The embodiment of table 1 and comparative example properties of product detection table
| Test event | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Density | 0.902 | 0.899 | 0.900 | |
| MFR | g/10min | 13.3 | 13.6 | 13.0 |
| Tensile strength | MPa | 27.3 | 26.8 | 26.2 |
| Elongation at break | % | 126 | 162 | 106 |
| Bending strength | MPa | 32.7 | 31.5 | 30.9 |
| The modulus of elasticity in static bending | MPa | 1406 | 1331 | 1290 |
| 23 DEG C of Izod notch impact strengths | kJ/m2 | 6.9 | 6.5 | 7.2 |
| - 20 DEG C of Izod notch impact strengths | kJ/m2 | 3.3 | 3.6 | 3.5 |
| Load deformation temperature | ℃ | 101 | 100 | 99 |
| Crystallization temperature | ℃ | 134 | 135 | 132 |
| Test event | Unit | Comparative example 1 | Comparative example 2 |
| Density | 0.901 | 0.900 | |
| MFR | g/10min | 13.1 | 11.2 |
| Tensile strength | MPa | 27.7 | 38.2 |
| Elongation at break | % | 56 | 67 |
| Bending strength | MPa | 30.5 | 37.8 |
| The modulus of elasticity in static bending | MPa | 1286 | 1740 |
| 23 DEG C of Izod notch impact strengths | kJ/m2 | 6.7 | 3.0 |
| - 20 DEG C of Izod notch impact strengths | kJ/m2 | 3.4 | - |
| Load deformation temperature | ℃ | 99 | 115 |
| Crystallization temperature | ℃ | 134 | 133 |
As it can be seen from table 1 the bending strength of composition of the invention, the modulus of elasticity in static bending, load deformation temperature, crystallization temperature
Deng the level for having reached a large amount of nucleator resulting compositions of addition, because nucleator addition is few, therefore with low cost
Advantage.
Claims (8)
1. a kind of high rigidity polypropene composition, it is characterised in that be made up of the raw material of following parts by weight：
Acrylic resin 100
Heat stabilizer 0.08 ~ 1.8
Metallic stearates 0.02 ~ 0.4
Inorganic filler 0.05 ~ 0.25
Organic nucleator 0.05 ~ 0.15.
2. high rigidity polypropene composition according to claim 1, it is characterised in that described acrylic resin is anti-impact
Acrylic resin copolymer.
3. high rigidity polypropene composition according to claim 1, it is characterised in that described heat stabilizer is hindered phenol
Kind antioxidant or/and phosphite ester kind antioxidant, Hinered phenols antioxidant are 1 with the weight ratio of phosphite ester kind antioxidant:0.1
~10。
4. high rigidity polypropene composition according to claim 3, it is characterised in that described Hinered phenols antioxidant is：
Four [methyl-β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic ester] pentaerythritol ester, β-（3,5- di-t-butyl -4- hydroxy benzenes
Base）The positive octadecanol ester of propionic acid, 1,3,5- trimethyls -2,4,6- three（3,5- di-tert-butyl-4-hydroxyl benzyls）Benzene or 2,2- sulphur
Dai Shuan [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate]；Described phosphite ester kind antioxidant is：Three（2,4-
Di-tert-butyl-phenyl）It is phosphite ester, double（2,4- DI-tert-butylphenol compounds）Pentaerythritol diphosphites or diphosphorous acid Ji Wusi
Alcohol distearyl alcohol ester.
5. high rigidity polypropene composition according to claim 1, it is characterised in that described Metallic stearates are hard
Resin acid zinc or calcium stearate, addition are 0.05 ~ 0.3 part.
6. high rigidity polypropene composition according to claim 1, it is characterised in that described inorganic filler be calcium carbonate,
Talcum powder, diatomite or mica, addition are 0.1 ~ 0.2 part.
7. high rigidity polypropene composition according to claim 1, it is characterised in that described organic nucleator is phosphorus
Acid metal salt class nucleator.
8. high rigidity polypropene composition according to claim 8, it is characterised in that described phosphate metal salt nucleation
Agent is nucleator HPN-68L, nucleant agent N A11 or nucleant agent N A21.
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| CN201610574025.1A CN106905614A (en) | 2016-07-20 | 2016-07-20 | A kind of high rigidity polypropene composition |
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| CN201610574025.1A CN106905614A (en) | 2016-07-20 | 2016-07-20 | A kind of high rigidity polypropene composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181117A (en) * | 2018-08-28 | 2019-01-11 | 中广核俊尔（上海）新材料有限公司 | A kind of low-density, high rigidity polypropylene material and preparation method thereof |
| CN111154175A (en) * | 2018-11-08 | 2020-05-15 | 昆山英诺特新材料有限公司 | Rigidity-enhanced polypropylene resin material |
| CN114605704A (en) * | 2022-02-08 | 2022-06-10 | 浙江兴越材料技术有限公司 | High-performance compound nucleating agent composition, polyolefin composition and plastic product |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952329A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
-
2016
- 2016-07-20 CN CN201610574025.1A patent/CN106905614A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952329A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181117A (en) * | 2018-08-28 | 2019-01-11 | 中广核俊尔（上海）新材料有限公司 | A kind of low-density, high rigidity polypropylene material and preparation method thereof |
| CN111154175A (en) * | 2018-11-08 | 2020-05-15 | 昆山英诺特新材料有限公司 | Rigidity-enhanced polypropylene resin material |
| CN114605704A (en) * | 2022-02-08 | 2022-06-10 | 浙江兴越材料技术有限公司 | High-performance compound nucleating agent composition, polyolefin composition and plastic product |
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