CN109401034A - A kind of self-reinforcing type foam polyolefin material and the preparation method and application thereof - Google Patents
A kind of self-reinforcing type foam polyolefin material and the preparation method and application thereof Download PDFInfo
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- CN109401034A CN109401034A CN201811216638.3A CN201811216638A CN109401034A CN 109401034 A CN109401034 A CN 109401034A CN 201811216638 A CN201811216638 A CN 201811216638A CN 109401034 A CN109401034 A CN 109401034A
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- type foam
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
Abstract
The invention discloses a kind of self-reinforcing type foam polyolefin materials and the preparation method and application thereof, conventional polyolefins material is partly or entirely substituted as self-reinforced material using linear low density polyethylene LLDPE and is prepared into high-intensitive foamed material, utilize its peculiar herring-bone form molecule microstructure (regular very short and small branched structure), increase tearing toughness, to reach the national standard of pulling force torsion, prepare the remote superstate toys standard (70N) of finished product pulling force torsional test, and improving pulling force torsion, tensile strength and it is elastic simultaneously, its hardness and regular-type foam ground cushion are similar, its service performance is not changed；Material is prepared without harmful substances such as formaldehyde, plasticizer, more leads to the problem of dioxin without chloride, safety and environmental protection performance is high；Preparation method can be used directly in primary producing line, not increase process flow, be suitble to industrialized production；Reduce production improving cost.
Description
Technical field
The present invention relates to foam material fields more particularly to a kind of self-reinforcing type foam polyolefin material and preparation method thereof
With application.
Background technique
Foamed material, which refers to, generates the substance that bubble makes the foaming of porous mass in substance internal gasifier, has weight
Light, specific strength height, excellent insulation performance, the advantage that buffer capacity is significant and adsorption capacity is strong are measured, has been widely used
In fields such as auto industry, building industry, packaging industry, agricultural, water process and air filtrations；Such as manufacture foamed plastics, bubble
Foam rubber, foamed resin etc..
" enhancing " is a kind of common technology of polymer matrix composite, using polymer as matrix, with fibrous strengthening material
Material is reinforcing agent." enhancing " greatly improves the intensity and other mechanical properties of high molecular material itself.Common reinforcing material
Have: glass fibre, carbon fiber, aramid fiber, natural fiber and metallic fiber etc..Glass fibre is handled with silane coupling agent,
The compatibility with polymer can be improved.For example carbon fiber enhancement resin base composite material has lightweight outstanding, Gao Biqiang, height
Than rigid and excellent fatigue strength, ambient stable performance, it is widely used in domestic and international aerospace industry and civil field.
The concept of " self-reinforcing " is originated from liquid crystal polymer, and original is a kind of enhancing side of the liquid crystal polyarylate as engineering plastics
Formula does not need addition reinforcing agent, has spontaneously formed the fibrous micro-structure of humidification in the structure and improved macromolecule
The intensity of material itself and other mechanical properties." self-reinforcing " refers exclusively to the humidification principle of LLDPE in this patent.Ethylene and few
Under the initiation for measuring (8~12%) C4~C8 alpha-olefin (such as 1- butylene) chromium and titanium fluoride catalysts, in pressure 0.7~
Coordination copolymerization is carried out at 12.1MPa and 85 DEG C~95 DEG C of temperature, and linea low density LLDPE is made.LLDPE have it is regular very
The special microstructure of short and small branched structure, since molecular separating force is larger, makes although crystallinity and density are similar to LDPE
Its certain performance such as tearing toughness, environmental stress crack resistance, paracentesis resistance etc. are better than LDPE and HDPE.Thus LLDPE pairs
Expanded polyolefin ground cushion has " self-reinforcing " effect.
The key property of polyolefin (mainly polyethylene or EVA) foam ground cushion applied to Crawl mat for children be it is soft and
There is certain elasticity, intensity especially tensile strength is without so important, and domestic and international expanded polyolefin ground cushion does not all carry out so far
Any enhancing processing.The tensile strength of polyethylene or EVA itself is not high, and foam ground cushion, intensity are just lower once being formed.Manufacture
Mass filler such as talcum powder when foam ground cushion in formula etc. not only without the intensity of raising polyethylene or EVA, reduces instead
Their tensile strength and other mechanical properties (in addition to improving hardness).
But since foam ground cushion is mainly used in infant, when mechanical property is unqualified, infant may pullled
With " small part " can be generated when baiting ground cushion, accidentally eat and damage.The product of current country's foam ground cushion industry is substantially
All do not reach the pulling force torsion national standard for limiting 70N (newton).Have become a big problem of puzzlement the sector.
Summary of the invention
Goal of the invention: In order to solve the problems of in the prior art, the invention proposes a kind of self-reinforcing type polyenes
Hydrocarbon foamed material and the preparation method and application thereof, the high-strength foaming materials being prepared, tensile strength and resilience are better than
The remote superstate standard of common ground cushion, especially pulling force torsion.
Technical solution: to achieve these objectives, the present invention takes following technical scheme:
A kind of self-reinforcing type foam polyolefin material, including as follows by weight prepare raw material: 100 parts of polyolefin,
10-12 parts of foaming agent, 0.5-5 parts of zinc oxide, 0.5-2 parts of stearic acid, 0.5-1.0 parts of crosslinking agent, 0-80 parts of filler；The polyene
Contain linear low density polyethylene LLDPE, degree 10%-100% in hydrocarbon；Its melt index MI value range is
1.0-4.0g/10min。
The present invention uses linear low density polyethylene LLDPE as self-reinforced material, micro- using its peculiar herring-bone form molecule
It sees structure (regular very short and small branched structure), increases tearing toughness, to reach the national standard of pulling force torsion.
More preferably, further include in the polyolefin melt index MI value range be 1.0-5.0g/10min low-density
Polyethylene LDPE, medium density polyethylene MDPE, metallocene PE MPE, vinyl-vinyl acetate copolymer EVA, polyolefin bullet
One of property body POE or a variety of.
Further, the foaming agent is azodicarbonamide, 4, at least one of 4 '-oxobenzenesulfonyl hydrazide.
Further, the crosslinking agent is two tert-butyl peroxy base diisopropylbenzene (DIPB)s, at least one in cumyl peroxide
Kind.
Further, the filler is talcum powder.
Disclosed herein as well is a kind of preparation methods of self-reinforcing type foam polyolefin material, include the following steps:
Required raw material is got ready on demand, is placed in internal rubber mixer and carries out mixing and plasticate processing, wherein closed refining glue
Built-in temperature is discharged after being the 130-140 DEG C of 10-30min that plasticates；The material of internal rubber mixer discharge is sent into open mill to carry out
The thin logical 10-20min of mill；It is cut after cooling in flakes, the foaming in 165-185 DEG C and cavity pressure 5-20MPa of press,
Obtain required self-reinforcing type foam polyolefin material.
The invention also discloses the applications of the high resiliency foamed material of above-mentioned preparation method preparation, especially by chemical blowing
It is prepared into one of ground cushion, coiled material.It is specifically as follows polyethylene ground cushion, eva foam ground cushion, LDPE foam ground cushion, PE
Foam ground cushion, mosaic floor, the products such as polyethylene coiled material material；It is mainly used for the sports such as Yoga place, infant climbs
Capable and playground, the elderly playground etc. is to ground cushion coiled material elasticity and the higher application of flexibility requirements.
The utility model has the advantages that a kind of self-reinforcing type foam polyolefin material provided by the invention and the preparation method and application thereof, with
The prior art, which is compared, has following advantages:
(1) the remote superstate toys standard (70N) of foamed material finished product pulling force torsional test of the invention.
(2) foamed material finished product tensile strength of the invention and the far super common foamed material of resilience.
(3) foamed material finished product of the invention improve pulling force torsion, tensile strength and it is elastic simultaneously, hardness with
Regular-type foam ground cushion is similar, does not change its service performance.
(4) material is prepared without harmful substances such as formaldehyde, plasticizer, more leads to the problem of dioxin without chloride, is pacified
Loopful guaranteed cost is high.
(5) preparation method can be used directly in primary producing line, not increase process flow, be suitble to industrialized production；It reduces
Produce improving cost.
Detailed description of the invention:
Fig. 1 is the strain-stress relation of the foamed material finished product of embodiment 5 (curve B) and comparative example 1 (curve A) preparation
Contrast schematic diagram；
Fig. 2 is the appearance diagram of polyethylene ground cushion prepared by embodiment 5；
Fig. 3 is the microscopic appearance (SEM photograph) of polyethylene ground cushion section prepared by embodiment 5.
Specific embodiment
Embodiment 1-5 and comparative example 1 are set: the foaming to the LLDPE preparation in polyolefin containing different quality ratio
Material carries out preparation test comparison, and wherein the total dosage of polyolefin is 3kg；It is specific as follows:
Embodiment 1:
A kind of self-reinforcing type foam polyolefin material, including as follows by weight prepare raw material: (melting refers to LLDPE
Number is 2.1g/10min) 0.6kg, LDPE (melt index 2.3g/10min) 2.4kg；Azodicarbonamide (AC) 305g, two
Tert-butylperoxyiso-propyl benzene (BIPB) 29g, stearic acid 25g, zinc oxide 27.5g, talcum powder 2kg.Wherein LDPE is specifically selected
Yangtze BASF 2426H, LLDPE specifically select the Relene of Reliance Industries Limited, in polyolefin
Mass percent is 20%.
Preparation method is as follows: required raw material got ready on demand, is placed in internal rubber mixer and is carried out mixing and plasticate processing,
Wherein temperature is 135 DEG C of 15min discharges of plasticating in internal rubber mixer；The material of internal rubber mixer discharge is sent into open mill
Carry out the thin logical 15min of mill；It is cut after cooling in flakes, the foaming in 175 DEG C of press obtains required self-reinforcing type polyolefin
Foamed material.
Embodiment 2- embodiment 5:
Remove that mass percentage content of the LLDPE in polyolefin is different, other prepare the type dosage of raw material with reality
It is identical to apply example 1；And preparation method is also same as Example 1, LLDPE specific mass percent in the polymer in embodiment 2-5
It is followed successively by 40%, 60%, 80%, 100%.
Comparative example 1:
A kind of common foamed material, including as follows by weight prepare raw material: low density polyethylene (Yangtze bar
This husband 2426H, melt index 2.3g/10min) 3kg, azodicarbonamide (AC) 305g, di-t-butyl peroxy isopropyl base benzene
(BIPB) 29g, stearic acid 25g, zinc oxide 27.5g, talcum powder 2kg.Difference with embodiment 1-5 is and is not added with LLDPE.
Finished product test comparison:
1) test method:
Pulling force torsion measuring method:
According to 6675.2-2014 " toy safety ", it is any on toy (ground cushion of creeping is a type toy) may be by children's thumb
Finger and index finger is caught or tooth is bitten toy protrusion or component should carry out following test.
Test article ground cushion is fixed by reasonable test position, is clipped ground cushion with fixture using torsional test.With torsion
Power meter or torque spanner apply (0.45 ± 0.02) Nm torsion to turning over 180 ° clockwise, then repeat counterclockwise above-mentioned
Test process.Tensile test is then completed on the same test position of the same component of torsional test.The precision of tensiometer is
±2N.Sample is fixed on a suitable position with suitable fixture, the main shaft of test component is parallel in 5s, is uniformly applied
Add the power of (70 ± 2) N and keeps 10s.
The measuring method of Shore A hardness:
According to GB/T530-1999 " the pocket hardometer penetration hardness test method of rubber ", international standard ISO7619:1986
It is tested, hardometer model are as follows: LX-A Shore durometer.
The measuring method of tensile strength:
Instrument is used according to GB/T6344-2008 " measurement of flexible foam polymeric material tensile strength and elongation at break "
Electronic universal tester model: Japanese Shimadzu AGS-X5KN.Specimen size is 152mm × 13mm × 10mm, and cross section is rectangle；
Tensile speed is 500mm/min ± 50mm/min；23 DEG C ± 2 DEG C of measuring temperature, relative humidity 50% ± 5%.
The measuring method of the coefficient of resilience:
According to GB/T6670-2008 " measurement of flexible foam polymeric material falling ball method resilience performance "；Corresponding international standard
ISO8307:2007.Steel ball falls height: 500mm after rise；Steel ball size: 16mm.Instrument model: (Dongguan City benefit opens up detector to KY-C
Device Co., Ltd).
Embodiment 1- embodiment 5 and comparative example 1 add the test data of the product of the LLDPE of different quality percentage such as
Shown in table 1:
Table 1: the properties of product comparison of the LLDPE preparation of different quality percentage is added in polyolefin
It is formed from table 1 it follows that 1-5 of the embodiment of the present invention is added to prepared by linear low density polyethylene LLDPE
Foamed material finished product hardness and comparative example 1 it is essentially identical, and pulling force torsional test is far beyond the 70N of national standard, most
190N, comparative example and not up to relevant criterion are up to arrived, and tensile strength is not added with the foamed material of LLDPE compared with comparative example 1
For it is more excellent；Have the superior coefficient of resilience, up to 36.7%.Therefore foamed material prepared by the present invention not only pulling force
The remote superstate toys standard (70N) of torsional test；And the far super common foamed material of tensile strength and resilience.
Furthermore please as shown in Figure 1 to the strain-stress relation contrast schematic diagram of embodiment 1 and comparative example 1.A is pair in figure
Ratio 1, B are embodiment 5.It can be seen that A is the load-deformation curve of typical plastic material, and B is typical elastic material
Load-deformation curve.The elongation at break of B ratio A is much bigger when stretching.
Additionally referring to shown in Fig. 2-Fig. 3, Fig. 2 is the appearance diagram of polyethylene ground cushion prepared by embodiment 5；Fig. 3
For the microscopic appearance (SEM photograph) of polyethylene ground cushion section prepared by embodiment 5.
Claims (7)
1. a kind of self-reinforcing type foam polyolefin material, it is characterised in that including as follows by weight prepare raw material: polyene
100 parts of hydrocarbon, 10-12 parts of foaming agent, 0.5-5 parts of zinc oxide, 0.5-2 parts of stearic acid, 0.5-1.0 parts of crosslinking agent, 0-80 parts of filler；
Contain linear low density polyethylene LLDPE, degree 10%-100% in the polyolefin；Its melt index MI value
Range is 1.0-4.0g/10min.
2. self-reinforcing type foam polyolefin material according to claim 1, it is characterised in that: also wrapped in the polyolefin
Include the low density polyethylene that melt index MI value range is 1.0-5.0g/10min, medium density polyethylene MDPE, metallocene
Polyethylene MPE, vinyl-vinyl acetate copolymer EVA, one of polyolefin elastomer or a variety of.
3. self-reinforcing type foam polyolefin material according to claim 1, it is characterised in that: the foaming agent is azo two
At least one of formamide, 4,4 '-oxobenzenesulfonyl hydrazide.
4. self-reinforcing type foam polyolefin material according to claim 1, it is characterised in that: the crosslinking agent is two tertiary fourths
At least one of peroxy diisopropylbenzene (DIPB), cumyl peroxide.
5. self-reinforcing type foam polyolefin material according to claim 1, it is characterised in that: the filler is talcum powder.
6. the preparation method of self-reinforcing type foam polyolefin material as described in claim 1, it is characterised in that including walking as follows
It is rapid:
Required raw material is got ready on demand, is placed in internal rubber mixer and carries out mixing and plasticate processing, wherein in internal rubber mixer
Temperature is discharged after being the 130-140 DEG C of 10-30min that plasticates；The material of internal rubber mixer discharge is sent into open mill and carries out mill
Thin logical 10-20min；It is cut after cooling in flakes, the foaming in 165-185 DEG C and cavity pressure 5-20MPa of press obtains
Required self-reinforcing type foam polyolefin material.
7. the application of the high-strength foaming materials of preparation method preparation as claimed in claim 6, it is characterised in that pass through chemistry
Foaming is prepared into one of ground cushion, coiled material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811216638.3A CN109401034A (en) | 2018-10-18 | 2018-10-18 | A kind of self-reinforcing type foam polyolefin material and the preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811216638.3A CN109401034A (en) | 2018-10-18 | 2018-10-18 | A kind of self-reinforcing type foam polyolefin material and the preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110216958A (en) * | 2019-05-24 | 2019-09-10 | 华南理工大学 | A kind of resistance to multi-layer foam material as well and preparation method thereof for drawing pressure resistance of lower thermal conductivity |
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|---|---|---|---|---|
| EP1088023B1 (en) * | 1998-06-10 | 2002-12-04 | Ht Troplast Ag | Method for producing foamed plastic blocks based on polyolefin |
| US20050288440A1 (en) * | 2004-06-21 | 2005-12-29 | Chou Richard T | Polyolefin foams for footwear foam applications |
| CN101402760A (en) * | 2008-08-25 | 2009-04-08 | 牟海妲 | Materials for making shoe soles and processing method |
| CN108314824A (en) * | 2018-03-05 | 2018-07-24 | 福建三盛实业有限公司 | A kind of XPE expanded materials and preparation method thereof |
-
2018
- 2018-10-18 CN CN201811216638.3A patent/CN109401034A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1088023B1 (en) * | 1998-06-10 | 2002-12-04 | Ht Troplast Ag | Method for producing foamed plastic blocks based on polyolefin |
| US20050288440A1 (en) * | 2004-06-21 | 2005-12-29 | Chou Richard T | Polyolefin foams for footwear foam applications |
| CN101402760A (en) * | 2008-08-25 | 2009-04-08 | 牟海妲 | Materials for making shoe soles and processing method |
| CN108314824A (en) * | 2018-03-05 | 2018-07-24 | 福建三盛实业有限公司 | A kind of XPE expanded materials and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110216958A (en) * | 2019-05-24 | 2019-09-10 | 华南理工大学 | A kind of resistance to multi-layer foam material as well and preparation method thereof for drawing pressure resistance of lower thermal conductivity |
| CN110216958B (en) * | 2019-05-24 | 2021-07-20 | 华南理工大学 | Low-thermal-conductivity tensile and pressure-resistant multilayer foaming material and preparation method thereof |
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Application publication date: 20190301 |