CN105400080B - A kind of damage resistant enhancing PP plastics and preparation method thereof - Google Patents
A kind of damage resistant enhancing PP plastics and preparation method thereof Download PDFInfo
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- CN105400080B CN105400080B CN201511008953.3A CN201511008953A CN105400080B CN 105400080 B CN105400080 B CN 105400080B CN 201511008953 A CN201511008953 A CN 201511008953A CN 105400080 B CN105400080 B CN 105400080B
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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
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08K3/36—Silica
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The invention discloses a kind of damage resistant enhancing PP plastics and preparation method thereof, the damage resistant enhancing PP plastics are prepared from by the raw material of following weight parts：90 110 parts of PP resins, 15 parts of graphite, 15 parts of calcium stearate, 5 15 parts of silica, 0.1 0.5 parts of coupling agent, 0.3 0.7 parts of damage resistant agent.A kind of damage resistant enhancing PP plastics of the present invention and preparation method thereof, by reasonably matching, preferably go out inorganic filler, the species of damage resistant agent and the consumption for being adapted to improve PP mechanical properties, improve scratch resistant performance and intensity.
Description
Technical field
The present invention relates to a kind of plastics and preparation method thereof, more particularly to a kind of damage resistant enhancing PP plastics and its preparation side
Method.
Background technology
Polypropylene (Poyropylene, PP) has been widely used in the packaging such as industry, agricultural, medical treatment, health and daily
In the every field of life, be that consumption is maximum in current world's high polymer material, a growth rate most fast class product, mainly
Because its raw material sources is more, price is low, material property is excellent, electrical insulating property and chemical stability are good, it is easy to add while have again
The advantage of work shaping.Although PP advantages are more, also have its not enough, be mainly shown as toughness, low temperature resistant, ageing-resistant performance compared with
Difference, and molding shrinkage is big, easy firing, simultaneously because its nonpolar feature, makes itself and other polar polymers, inorganic filler
Compatibility it is poor, so as to limit the raw material as products such as injection, fiber, films or the application of PP Pipe Compound.Therefore, in order to
Expand PP application field, it is necessary to PP is modified, its performance is improved.
Whether chemically reacted by modification, polyacrylic method of modifying can be divided into physical modification and chemistry changes
Property；It can be divided into Blending Toughening Modification, filling enhancing modified, functional modification and flame-retardant modified by using function.Polyacrylic thing
Reason is modified main by adding other polymer, filler and compatilizer, and reaching improves the purpose of material property, including blending changes
Property, inorganic particulate activeness and quietness is modified and flame-retardant modified etc..Polyolefin blends are studied and application has obtained academia and work
The extensive concern of industry and develop rapidly.
The simplest method of polymer modification is the filling-modified of inorganic particulate.By size, inorganic particulate can divide
For micro particles, nano-particle and the class of whisker particle three.The filling-modified method of inorganic particulate can not only improve the firm of polymer
Degree, hardness, modulus, impact flexibility and heat distortion temperature, moreover it is possible to reduce cost.Due to the intensity and toughness of polymer composites
Mainly influenceed, therefore increased using interface with interparticle interface binding intensity by the particle diameter of filler grain, shape and matrix
Tough dose or elastomer etc. and the common activeness and quietness PP of inorganic rigid particle, can effectively improve toughness of material, while making material also have
There is higher intensity, finally realize PP enhancings and toughness reinforcing.From there through by the fine of inorganic particulate, nanosizing and function of surface
Change, filler is changed into functional stuffing, cooperate with the strength and toughness of increase polymer to be filled out as polymer/inorganic with elastomer
Expect the study hotspot of composite.
Micro inorganic rigid particles improve PP toughness, can be while its tensile strength and rigidity is not reduced, moreover it is possible to
Improve material erosion-resisting characteristics and heat distortion temperature.Nanometer material and technology rises since 1990s, gradually makes inorganic
Filler grain develops to nanosizing and functionalization direction.Nano-particles filled polymer must realize that nano-particle exists with polymer
It is dispersed on nanoscale, it can be only achieved preferably enhancing, toughening effect.Therefore, using nanometer particle-modified polymer,
Appropriate surface treatment should be carried out, the surface energy of particle is reduced, and increases the interface in plasticizing process between particle and matrix
Interaction, improves mechanical shear stress, is finally reached the dispersed effect of nano-particle.
Strengthen PP plastics the invention provides a kind of damage resistant, intensity is high, and with excellent scratch resistant performance.
The content of the invention
For above shortcomings in the prior art, one of technical problems to be solved by the invention are to provide a kind of resistance to
Scratch enhancing PP plastics.
The two of the technical problems to be solved by the invention, which are to provide a kind of damage resistant, strengthens the preparation method of PP plastics.
The present invention seeks to what is be achieved through the following technical solutions：
A kind of damage resistant strengthens PP plastics, is prepared from by the raw material of following weight parts：
90-110 parts of PP resins, 1-5 parts of graphite, 1-5 parts of calcium stearate, 5-15 parts of silica, coupling agent 0.1-0.5
Part, 0.3-0.7 parts of damage resistant agent.
Preferably, described coupling agent is selected from silane coupler, titanate coupling agent, aluminate coupling agent, zirconate idol
Join mixtures one or more in agent.
It is highly preferred that described coupling agent is by 40-60wt%3- acryloxypropyls dimethoxysilane and 40-
60wt%3- [oxygen of (2,3)-epoxy third] hydroxypropyl methyl dimethoxysilane is mixed.
Preferably, described damage resistant agent is by 40-60wt%N, N- dimethyl lauramide and 40-60wt%N, N- diethyl
Base lauramide is mixed.
Preferably, described silica is nano silicon, and particle diameter is 10-50nm.
Obviously, other performances in the present invention for raising product, add to the property of may also adapt to other auxiliary agents, such as fire-retardant
Agent, colouring agent and antistatic additive etc..
Colouring agent can be ultramarine blue, permanent yellow, G cadmium scarlet, phthalocyanine blue, phthalocyanine blue, carbon black, titanium white, manganese violet etc..Can
To be directly added into colouring agent after each component is mixed, then it is transferred in screw extruder, extruding pelletization, the ABS after being coloured
Plastics.The ABS plastic obtained using various colouring agents, is respectively provided with preferable damage resistant effect.
Present invention also offers the preparation method that above-mentioned damage resistant strengthens PP plastics, comprise the following steps：
(1) it is silica modified：Silica and coupling agent are mixed with improved silica；
(2) improved silica, PP resins, graphite, calcium stearate, damage resistant agent are well mixed, mixing plasticizing, extrusion
Granulation.
Preferably, step (1) silica stirs 15- in high speed mixing machine with coupling agent at a temperature of 75-85 DEG C
25min is well mixed, and obtains improved silica.
Preferably, the step (2) is adds in double screw extruder, and the processing temperature of double screw extruder is 190-
270 DEG C, engine speed is cooling check rod, air-dried pelletizing after 300-400 revs/min, extrusion.
A kind of damage resistant enhancing PP plastics of the present invention and preparation method thereof, by reasonably matching, preferably go out suitable
Inorganic filler, the species of damage resistant agent and the consumption of PP mechanical properties are improved, scratch resistant performance and intensity is improved.
Damage resistant enhancing PP plastics of the present invention have good combination property, can be widely applied to automotive upholstery such as instrument
Plate, column, glove compartment, door-plate etc., exterior trimming parts such as bumper, chafing strip, spoiler etc..
Embodiment
With reference to embodiment, the present invention is described further, as described below, is only the preferable implementation to the present invention
Example, not does the limitation of other forms, any those skilled in the art are possibly also with the disclosure above to the present invention
Technology contents be changed to the equivalent embodiment changed on an equal basis.It is every without departing from the present invention program content, according to the present invention
Technical spirit any simple modification that following examples are made or equivalent variations, all fall within protection scope of the present invention.
Each raw material introduction in embodiment：
PP resins：No. CAS：9003-07-0, the board produced using China Petroleum ＆ Chemical Co., Ltd. Maoming Branch
Number be N-T30S acrylic resin.
3- acryloxypropyl dimethoxysilanes, No. CAS：13732-00-8.
3- [oxygen of (2,3)-epoxy third] hydroxypropyl methyl dimethoxysilane, No. CAS：65799-47-5.
Silica, No. CAS：7631-86-9, particle diameter is 15-25nm.
N, N- dimethyl lauramide, No. CAS：3007-53-2.
N, N- diethyl lauramide, No. CAS：3352-87-2.
Graphite, No. CAS：7782-42-5, particle diameter is 15-25nm.
Calcium stearate, No. CAS：1592-23-0.
Ultramarine blue is added in embodiment as the purpose of colouring agent is, to measure table before and after scratch using colorimeter
Face colo(u)r bias △ E, investigate scratch resistant performance.
Embodiment 1
Weigh each raw material (parts by weight)：100 parts of PP resins, 2 parts of graphite, 2 parts of calcium stearate, 0 part of silica 1, coupling
0.2 part of agent, 0.4 part of damage resistant agent, 0.3 part of ultramarine blue.
Described coupling agent is by 0.1 part of 3- acryloxypropyls dimethoxysilane and 0.1 part of 3- [(2,3)-ring
The oxygen of oxygen third] hydroxypropyl methyl dimethoxysilane mixes.
Described damage resistant agent is by 0.2 part of N, N- dimethyl lauramide and 0.2 part of N, the mixing of N- diethyl lauramide
Form.
(1) it is silica modified：Silica is stirred into 20min in high speed mixing machine with coupling agent at a temperature of 80 DEG C mix
Close uniform, obtain improved silica；
(2) improved silica, PP resins, graphite, calcium stearate, damage resistant agent, ultramarine blue are well mixed, added double
In screw extruder, 240 DEG C of the processing temperature of double screw extruder, engine speed is 350 revs/min；Check rod, wind are cooled down after extrusion
Dry pelletizing, that is, prepare damage resistant enhancing PP plastics of the present invention.
Embodiment 2
Damage resistant enhancing PP plastics are prepared by the raw material proportioning and method of embodiment 1, are differed only in：Described coupling agent
For 0.2 part of 3- acryloxypropyl dimethoxysilane.Obtain the damage resistant enhancing PP plastics of embodiment 2.
Embodiment 3
Damage resistant enhancing PP plastics are prepared by the raw material proportioning and method of embodiment 1, are differed only in：Described coupling agent
For 0.2 part of 3- [oxygen of (2,3)-epoxy third] hydroxypropyl methyl dimethoxysilane.Obtain the damage resistant enhancing PP plastics of embodiment 3.
Embodiment 4
Damage resistant enhancing PP plastics are prepared by the raw material proportioning and method of embodiment 1, are differed only in：Described damage resistant
Agent is 0.4 part of N, N- dimethyl lauramides.Obtain the damage resistant enhancing PP plastics of embodiment 4.
Embodiment 5
Damage resistant enhancing PP plastics are prepared by the raw material proportioning and method of embodiment 1, are differed only in：Described damage resistant
Agent is 0.4 part of N, N- diethyl lauramides.Obtain the damage resistant enhancing PP plastics of embodiment 5.
Test case 1
The traditional performance of the damage resistant enhancing PP plastics prepared to embodiment 1-5 is tested.Specific test result
It is shown in Table 1：
Table 1：Damage resistant strengthens PP plastics traditional performance test datas
Comparing embodiment 1 and embodiment 2-3, in the case of coupling agent adds total amount identical, (the 3- acryloyls of embodiment 1
Epoxide hydroxypropyl methyl dimethoxysilane and 3- [oxygen of (2,3)-epoxy third] hydroxypropyl methyl dimethoxysilane compounding) damage resistant increasing
The traditional performance of strong PP plastics be substantially better than embodiment 2-3 (3- acryloxypropyls dimethoxysilane and 3- [(2,
3)-oxygen of epoxy third] single raw material in hydroxypropyl methyl dimethoxysilane).
Test case 2
Embodiment 1-5 damage resistant enhancing PP plastics scratch resistant performances are tested.
The method of testing of scratch resistant performance is to evaluate scuffing degree using scuffing tester.With the scraper of a Mechanical Driven
A line segment figure is scraped in damage resistant enhancing PP frostings.Each scraper is only scraped once in one direction.Then utilize
One colorimeter measures the misalignment △ E that non-surface scratch is compared.
Test condition is：
Temperature：23 ± 5 DEG C, support force：10N, scratches speed：1000mm/min, scraper diameter：1mm.
Table 1：Scratch resistant performance tests table
| Aberration △ E after scuffing | |
| Embodiment 1 | 0.11 |
| Embodiment 2 | 0.15 |
| Embodiment 3 | 0.17 |
| Embodiment 4 | 0.26 |
| Embodiment 5 | 0.24 |
Comparing embodiment 1 and embodiment 4-5, in the case of damage resistant agent adds total amount identical, (N, the N- bis- of embodiment 1
Methyl lauramide and N, N- diethyl lauramide compounding) damage resistant enhancing PP plastics scratch resistant performance be substantially better than implementation
Example 4-5 (single raw material in N, N- dimethyl lauramide and N, N- diethyl lauramide).
Claims (6)
1. a kind of damage resistant strengthens PP plastics, it is characterised in that be prepared from by the raw material of following weight parts：PP resins 90-110
Part, 1-5 parts of graphite, 1-5 parts of calcium stearate, 5-15 parts of silica, 0.1-0.5 parts of coupling agent, 0.3-0.7 parts of damage resistant agent；
Described coupling agent by 40-60wt%3- acryloxypropyls dimethoxysilane and 40-60wt%3- [(2,
3)-oxygen of epoxy third] hydroxypropyl methyl dimethoxysilane mixes.
2. damage resistant as claimed in claim 1 strengthens PP plastics, it is characterised in that described damage resistant agent is by 40-60wt%
N, N- dimethyl lauramide and 40-60wt%N, N- diethyl lauramide are mixed.
3. damage resistant as claimed in claim 1 strengthens PP plastics, it is characterised in that described silica is nanometer titanium dioxide
Silicon, particle diameter is 10-50nm.
4. the damage resistant as described in claim any one of 1-3 strengthens the preparation method of PP plastics, it is characterised in that including following
Step：
(1) it is silica modified：Silica and coupling agent are mixed with improved silica；
(2) improved silica, PP resins, graphite, calcium stearate, damage resistant agent are well mixed, mixing plasticizing, extrusion is made
Grain.
5. damage resistant as claimed in claim 4 strengthens the preparation method of PP plastics, it is characterised in that step (1) dioxy
SiClx stirs 15-25min in high speed mixing machine with coupling agent and is well mixed at a temperature of 75-85 DEG C, obtain improved silica.
6. damage resistant as claimed in claim 4 strengthens the preparation method of PP plastics, it is characterised in that the step (2) is to add
Enter in double screw extruder, the processing temperature of double screw extruder is 190-270 DEG C, and engine speed is 300-400 revs/min, is squeezed
Check rod is cooled down after going out, pelletizing is air-dried.
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| CN108610553A (en) * | 2018-04-20 | 2018-10-02 | 苏州睿烁环境科技有限公司 | A kind of damage resistant PP plastics and its preparation method and application |
| CN113637261A (en) * | 2021-09-23 | 2021-11-12 | 广东腾熙科技咨询有限公司 | Scratch-resistant reinforced PP plastic and preparation method thereof |
| CN115028916A (en) * | 2022-06-08 | 2022-09-09 | 广州丽盈塑料有限公司 | High-barrier light plastic for plastic packaging container and preparation method thereof |
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| CN1986627A (en) * | 2005-12-22 | 2007-06-27 | 吴永刚 | Composite polypropylene material and its preparing method |
| CN102020805B (en) * | 2009-09-10 | 2012-07-18 | 中国石油化工股份有限公司 | Polypropylene resin composition and preparation method thereof |
| CN102532686A (en) * | 2010-12-23 | 2012-07-04 | 上海普利特复合材料股份有限公司 | Low-gloss and scratch-resistant polypropylene material and preparation method thereof |
| CN103131086A (en) * | 2011-12-02 | 2013-06-05 | 合肥杰事杰新材料股份有限公司 | Scraping-resistant polypropylene combination with good appearance and manufacturing method and application thereof |
| CN103319781B (en) * | 2012-03-22 | 2016-12-28 | 住友化学株式会社 | Propylene resin composition and injection molded article thereof |
| CN102807711B (en) * | 2012-08-23 | 2014-03-12 | 上海瀚氏模具成型有限公司 | Scratching-resistant polypropylene material and preparation method thereof |
| CN103571058A (en) * | 2013-11-22 | 2014-02-12 | 苏州润佳工程塑料股份有限公司 | Reinforced scratching-resistant polypropylene material |
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Inventor after: Zhang Rongfu Inventor after: Yin Ling Inventor after: Lu Yiming Inventor after: Zhou Yafei Inventor before: Chen Bin Inventor before: Zhang Rongfu Inventor before: Yin Ling Inventor before: Zhao Yahong Inventor before: Lu Yiming |
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Effective date of registration: 20171124 Address after: 430200 No. twelve workshop in the three phase of the Da Hua Ling industrial garden, Jiangxia District, Wuhan City, Hubei Patentee after: Hubei Han Beijing Great Automotive Components Company Limited Address before: 201100 Shanghai City, Xhenzhuang Town, East Road, No. 355 friends Patentee before: Shanghai HAN's Mould Shape Co., Ltd. |