CN106854309A - A kind of low smell modified polypropylene composite material and preparation method thereof - Google Patents
A kind of low smell modified polypropylene composite material and preparation method thereof Download PDFInfo
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- CN106854309A CN106854309A CN201611173292.4A CN201611173292A CN106854309A CN 106854309 A CN106854309 A CN 106854309A CN 201611173292 A CN201611173292 A CN 201611173292A CN 106854309 A CN106854309 A CN 106854309A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention belongs to technical field of polymer composite materials, and in particular to a kind of low smell modified polypropylene composite material and preparation method thereof.The composite includes polypropylene：35 87 parts；Water-absorbing resin：35 parts；Inorganic mineral powder：0 40 parts；Toughener：10 20 parts；Processing aid：0.3 1.0 parts；Heat stabilizer master batch：0.2 0.8 parts；Ozone Water：46 parts.Present invention introduces Ozone Water, the low molecule such as the oxidable low molecule aldehyde of ozone, ketone, amine and benzene class activity odoring substance, can improve PP composite material smell at high temperature, reduce VOC content；Present invention introduces ozone water solution, aqueous solution vaporization at high temperature produces a large amount of vapor, forms overcritical under melt pressure, can further extract low molecule in PP composite material, improves PP composite material smell, reduces VOC content.
Description
Technical field
The invention belongs to technical field of polymer composite materials, and in particular to a kind of low smell modified polypropylene composite material
And preparation method thereof.
Technical background
With the raising of the health, environmental consciousness of people, to peculiar smell in passenger car and aldehydes, benzene class, fat hydrocarbon eutectic
The complaint of point volatile harmful material (abbreviation VOC) is increasing, the eve in this year " 3.15 ", and State General Administration for Quality Supervision has issued in the past
In 1 year consumer about vehicle product quality complaint, new car in-car air quality turned into complain four large focal spot problems it
It is first.
The fast development of polypropylene modification technology so that the application in automobile interior exterior decorations is more and more extensive, yet with
Polypropylene is influenceed in building-up process by monomer, catalyst, polymerization technique and degraded etc., and acrylic resin and its product are still deposited
It is healthy in release volatile organic matter (VOC) pollution environment and harm people to some extent, it is subject in actual use
Many limitations.
The content of the invention
The technical problems to be solved by the invention are the defects for overcoming prior art, there is provided a kind of low smell modified polypropene
The preparation method of composite.
In order to achieve the above object, the present invention is realized by following technical proposal：
A kind of low smell modified polypropylene composite material, the weight portion of its constitutive material is：
The polypropylene is at least one in homopolymerization polypropylene, COPP, and it is in 230 DEG C of temperature and load
Melt index under the conditions of 2.16kg is 3-100g/10min.
The water-absorbing resin is in carboxymethylated cellulosic, hydroxypropylation cellulose, shitosan, methylolation starch
Plant or two or more mixtures.
The inorganic mineral powder is at least one of talcum powder, calcium carbonate, glass, whisker, wollastonite.
The toughener is vinyl elastomer or styrenic elastomer.
The processing aid is selected from low molecular hydrocarbon, metal soap, stearic acid compound esters and amide-type processing aid
At least one.
The heat stabilizer master batch is selected from least one in Hinered phenols, hindered amines, phosphite ester type thermal stabilizing agent
Master batch.
The Ozone Water is the 0.1-10mg/kg aqueous solution of ozone.
The method for preparing above-mentioned a kind of low smell modified polypropylene composite material, comprises the following steps：
(1) odor adsorption material is prepared：
Water-absorbing resin in formula and Ozone Water are put into low mixed machine, 5-10min is mixed at 20-30 DEG C, be obtained
Odor adsorption material；
(2) preparation of composite：
Polypropylene, odor adsorption material, inorganic mineral powder, toughener, processing aid are carried out by weight ratio in formula
It is 35-50 in draw ratio after well mixed：Melted in 1 double screw extruder, mixed, disperseed, then heat stabilizer is female
Grain is added from the side feeding of double screw extruder, is plastified at a temperature of 170-210 DEG C, then by double-screw extruding pelletizing,
Just obtain low smell modified polypropylene composite material.
The beneficial effects of the present invention are：
1) present invention introduces ozone, the low molecules such as low molecule aldehyde, ketone, amine and benzene class activity smell thing is aoxidized at high temperature
Matter, can improve PP composite material smell, reduce VOC content；
2) present invention introduces ozone, decompose produce oxygen at high temperature, can be escaped through natural exhaust outlet；
3) present invention introduces ozone water solution, aqueous solution vaporization at high temperature produces a large amount of vapor, under melt pressure
Form overcritical, can further extract low molecule in PP composite material, improve PP composite material smell, reduce VOC
Content.
Specific embodiment：
Embodiment is given below to be specifically described with to the present invention, it is necessary to it is pointed out here that be following examples only
It is used to further illustrate the present invention, it is impossible to be interpreted as limiting the scope of the invention, the field is skilled in technique
Personnel still fall within protection scope of the present invention according to some nonessential modifications and adaptations that present invention is made to the present invention.
All compositions of the invention are existing commercially available prod, wherein：
Toughener is vinyl elastomer or styrenic elastomer, such as polyethylene (PE), ethylene-octene copolymer
(POE), ethylene-propylene-diene terpolymer (EPDM) etc..
Processing aid is selected from the compound esters of low molecular hydrocarbon, metal soap, stearic acid and amide-type processing aid extremely
Few one kind.Refer mainly to calcium stearate (Ca-St2), ethylene bis stearamide (EBS), modified ethylene bis stearamide (TAF) etc..
Heat stabilizer is selected from least one in Hinered phenols, hindered amines, phosphorous acid esters, and wherein Hinered phenols heat is steady
Determining agent has 2,6- three-level butyl -4- methylphenols, double (3,5- three-level butyl -4- hydroxy phenyls) thioethers or four (β-(3,5- three-levels
Butyl -4- hydroxy phenyls) propionic acid) master batch such as pentaerythritol ester (1010)；Phosphite type thermal stabilizing agent has three (2,4- bis- tertiary fourths
Base phenyl) phosphite ester (168), three monooctyl esters, three last of the ten Heavenly stems esters or three (Lauryl Alcohol) esters and three (16 carbon alcohol) esters；Hindered amines heat
Stabilizer has the master batches such as naphthylamines, diphenylamines, p-phenylenediamine.
In the present invention, the preparation of low smell modified polypropylene composite material uses following methods：
(1) odor adsorption material is prepared：
Water-absorbing resin in formula and Ozone Water are put into low mixed machine, 5-10min is mixed at 20-30 DEG C, be obtained
Odor adsorption material；
(2) preparation of composite：
Polypropylene, odor adsorption material, inorganic mineral powder, toughener, processing aid are carried out by weight ratio in formula
It is 35-50 in draw ratio after well mixed：Melted in 1 double screw extruder, mixed, disperseed, then heat stabilizer is female
Grain is added from the side feeding of double screw extruder, is plastified at a temperature of 170-210 DEG C, then by double-screw extruding pelletizing,
Just obtain low smell modified polypropylene composite material.
First, the formula and preparation parameter of embodiment and comparative example
Following specific embodiment 1-5 is to be prepared low smell modified polypropene using above-mentioned preparation method to be combined
Material, does not make tired stating.
Embodiment 1：
First be put into low mixed machine for water-absorbing resin in formula and Ozone Water by the present embodiment, and 5- is mixed at 20-30 DEG C
10min, is obtained odor adsorption material；It is 50 to use draw ratio again:1 double screw extruder, by polypropylene, odor adsorption material,
Inorganic mineral powder, toughener, processing aid are melted in this extruder, mixed, disperseed, finally by heat stabilizer master batch from double
The side feeding of screw extruder is added, and is plastified at a temperature of 170-210 DEG C and extruding pelletization obtains final product product.
Embodiment 2：
First be put into low mixed machine for water-absorbing resin in formula and Ozone Water by the present embodiment, and 5- is mixed at 20-30 DEG C
10min, is obtained odor adsorption material；It is 35 to use draw ratio again:1 double screw extruder, by polypropylene, odor adsorption material,
Inorganic mineral powder, toughener, processing aid are melted in this extruder, mixed, disperseed, finally by thermally-stabilised master batch from double spiral shells
The side feeding of bar extruder is added, and is plastified at a temperature of 170-210 DEG C and extruding pelletization obtains final product product.
Embodiment 3：
First be put into low mixed machine for water-absorbing resin in formula and Ozone Water by the present embodiment, and 5- is mixed at 20-30 DEG C
10min, is obtained odor adsorption material；It is 40 to use draw ratio again:1 double screw extruder, by polypropylene, odor adsorption material,
Inorganic mineral powder, toughener, processing aid are melted in this extruder, mixed, disperseed, finally by heat stabilizer master batch from double
The side feeding of screw extruder is added, and is plastified at a temperature of 170-210 DEG C and extruding pelletization obtains final product product.
Embodiment 4：
First be put into low mixed machine for water-absorbing resin in formula and Ozone Water by the present embodiment, and 5- is mixed at 20-30 DEG C
10min, is obtained odor adsorption material；It is 40 to use draw ratio again:1 double screw extruder, by polypropylene, odor adsorption material,
Inorganic mineral powder, toughener, processing aid are melted in this extruder, mixed, disperseed, finally by heat stabilizer master batch from double
The side feeding of screw extruder is added, and is plastified at a temperature of 170-210 DEG C and extruding pelletization obtains final product product.
Embodiment 5：
First be put into low mixed machine for water-absorbing resin in formula and Ozone Water by the present embodiment, and 5- is mixed at 20-30 DEG C
10min, is obtained odor adsorption material；It is 40 to use draw ratio again:1 double screw extruder, by polypropylene, odor adsorption material,
Inorganic mineral powder, toughener, processing aid are melted in this extruder, mixed, disperseed, finally by heat stabilizer master batch from double
The side feeding of screw extruder is added, and is plastified at a temperature of 170-210 DEG C and extruding pelletization obtains final product product.
Comparative example 1：
It is 40 that this comparative example uses draw ratio:1 double screw extruder, by polypropylene, water-absorbing resin, inorganic mineral powder, toughness reinforcing
Agent, processing aid are melted in this extruder, mixed, disperseed, then by heat stabilizer master batch from the side of double screw extruder
Feeding is added, and is plastified at a temperature of 170-210 DEG C and extruding pelletization obtains final product product.
Comparative example 2：
It is 40 that this comparative example uses draw ratio:1 double screw extruder, by polypropylene, water-absorbing resin, inorganic mineral powder, toughness reinforcing
Agent, processing aid are melted in this extruder, mixed, disperseed, then by heat stabilizer master batch from the side of double screw extruder
Feeding is added, and is plastified at a temperature of 170-210 DEG C and extruding pelletization obtains final product product.
2nd, the test result of embodiment and comparative example
Carried out after above-described embodiment 1-5 and sample obtained in comparative example 1-2 are molded into standard batten according to unified technique
Test, the testing standard of wherein tensile strength is ISO527/2-93, units MPa；Bending modulus testing standard is ISO178/2-
93, units MPa；23 DEG C of notch impact strength testing standards are ISO179/2-93, unit kJ/m2.Smell judgment criteria is divided into：1
Level：Odorlessness, 2 grades：It is odorous, but non interference smell, 3 grades：There are obvious smell, but non interference smell, 4 grades：There is interference
Property smell, 5 grades：There are strong interference smell, 6 grades：There is insupportable smell.VOC testing standard TS-BD-003-2012, survey
Pilot production 2000L sack methods.Its specific physical index is as shown in the table：
Table 1：Embodiment and comparative example physical data
Modified polypropylene composite material is can be seen that from the data of embodiment 1-5 and comparative example 1-2 meet automobile main frame maker
Requirement to smell≤3.5 rank, meanwhile, it has been greatly reduced TVOC and benzene class, the content of aldehydes low molecular weight volatile thing.
The above implementation method is only that the preferred embodiment of the present invention is described, not to model of the invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to technical side of the invention
Various modifications and improvement that case is made, all should fall into the protection domain of claims of the present invention determination.
Claims (9)
1. a kind of low smell modified polypropylene composite material, it is characterised in that：The weight portion of its constitutive material is：
Polypropylene：35-87 parts；
Water-absorbing resin：3-5 parts；
Inorganic mineral powder：0-40 parts；
Toughener：10-20 parts；
Processing aid：0.3-1.0 parts；
Heat stabilizer master batch：0.2-0.8 parts；
Ozone Water：4.0-6.0 parts.
2. a kind of low smell modified polypropylene composite material according to claim 1, it is characterised in that：The polypropylene is
At least one in homopolymerization polypropylene, COPP, it is for 230 DEG C with the melt index under the conditions of load 2.16kg in temperature
3-100g/10min。
3. a kind of low smell modified polypropylene composite material according to claim 1, it is characterised in that：The water-absorbing resin
It is one or more the mixing in carboxymethylated cellulosic, hydroxypropylation cellulose, shitosan, methylolation starch
Thing.
4. a kind of low smell modified polypropylene composite material according to claim 1, it is characterised in that：The inorganic mineral powder
It is at least one of talcum powder, calcium carbonate, glass, whisker, wollastonite.
5. a kind of low smell modified polypropylene composite material according to claim 1, it is characterised in that：The toughener is
Vinyl elastomer or styrenic elastomer.
6. a kind of low smell modified polypropylene composite material according to claim 1, it is characterised in that：The processing aid
Selected from least one in low molecular hydrocarbon, metal soap, stearic acid compound esters and amide-type processing aid.
7. a kind of low smell modified polypropylene composite material according to claim 1, it is characterised in that：The heat stabilizer
Master batch is selected from least one master batch in Hinered phenols, hindered amines, phosphite ester type thermal stabilizing agent.
8. a kind of low smell modified polypropylene composite material according to claim 1, it is characterised in that：The Ozone Water is
The 0.1-10mg/kg aqueous solution of ozone.
9. a kind of method for preparing low smell modified polypropylene composite material as claimed in claim 1, it is characterised in that：Including with
Lower step：
（1）Prepare odor adsorption material：
Water-absorbing resin in formula and Ozone Water are put into low mixed machine, 5-10min is mixed at 20-30 DEG C, smell is obtained
Sorbing material；
（2）The preparation of composite：
Polypropylene, odor adsorption material, inorganic mineral powder, toughener, processing aid are mixed by weight ratio in formula
It is 35-50 in draw ratio after uniform：Melted in 1 double screw extruder, mixed, disperseed, then by heat stabilizer master batch
Added from the side feeding of double screw extruder, plastified at a temperature of 170-210 DEG C, then by double-screw extruding pelletizing, just
Obtain low smell modified polypropylene composite material.
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| CN201611173292.4A CN106854309B (en) | 2016-12-18 | 2016-12-18 | Low-odor modified polypropylene composite material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109081925A (en) * | 2018-07-02 | 2018-12-25 | 苏州旭光聚合物有限公司 | A kind of supercritical fluid green method efficiently removing smell and VOCs in plastics simultaneously |
| CN109608809A (en) * | 2018-12-07 | 2019-04-12 | 广州市聚赛龙工程塑料股份有限公司 | A kind of low odor polypropylene composite material and preparation method thereof |
| CN112920504A (en) * | 2019-12-05 | 2021-06-08 | 苏州荣昌复合材料有限公司 | Ultralow-odor reinforced polypropylene composite material and preparation method thereof |
| CN115431433A (en) * | 2022-08-11 | 2022-12-06 | 北方华锦化学工业股份有限公司 | Device and process for preparing low-VOC-content ABS resin by using water as supercritical fluid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571054A (en) * | 2013-10-24 | 2014-02-12 | 合肥会通新材料有限公司 | Low VOC polypropylene composite material and preparation and application thereof |
-
2016
- 2016-12-18 CN CN201611173292.4A patent/CN106854309B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571054A (en) * | 2013-10-24 | 2014-02-12 | 合肥会通新材料有限公司 | Low VOC polypropylene composite material and preparation and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109081925A (en) * | 2018-07-02 | 2018-12-25 | 苏州旭光聚合物有限公司 | A kind of supercritical fluid green method efficiently removing smell and VOCs in plastics simultaneously |
| CN109608809A (en) * | 2018-12-07 | 2019-04-12 | 广州市聚赛龙工程塑料股份有限公司 | A kind of low odor polypropylene composite material and preparation method thereof |
| CN109608809B (en) * | 2018-12-07 | 2021-05-25 | 广州市聚赛龙工程塑料股份有限公司 | Low-odor polypropylene composite material and preparation method thereof |
| CN112920504A (en) * | 2019-12-05 | 2021-06-08 | 苏州荣昌复合材料有限公司 | Ultralow-odor reinforced polypropylene composite material and preparation method thereof |
| CN115431433A (en) * | 2022-08-11 | 2022-12-06 | 北方华锦化学工业股份有限公司 | Device and process for preparing low-VOC-content ABS resin by using water as supercritical fluid |
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