CN107522891A - A kind of method by performed polymer expanded polypropylene foamed plastics - Google Patents
A kind of method by performed polymer expanded polypropylene foamed plastics Download PDFInfo
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- CN107522891A CN107522891A CN201710705951.2A CN201710705951A CN107522891A CN 107522891 A CN107522891 A CN 107522891A CN 201710705951 A CN201710705951 A CN 201710705951A CN 107522891 A CN107522891 A CN 107522891A
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- performed polymer
- propylene
- foamed plastics
- expanded polypropylene
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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
-
- 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
-
- 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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Abstract
The present invention relates to technical field of macromolecules, more particularly to a kind of method by performed polymer expanded polypropylene foamed plastics, the method by performed polymer expanded polypropylene foamed plastics, comprises the following steps：（1）Propylene monomer and catalyst are well mixed in a solvent, then carry out prepolymerization in a kettle, obtains propylene performed polymer；（2）Propylene performed polymer, propylene, foaming agent, catalyst and auxiliary agent are added in mould, pouring molding is carried out, obtains pre-product；（3）Prepolymer is foamed at 164 ~ 170 DEG C, obtains polypropylene foam.In the present invention first under the conditions of existing for catalyst, propylene monomer is subjected to prepolymerization reaction in a solvent, then after performed polymer is mixed with propylene monomer, foamed during polymerization, the melt strength low intensity firmly believed, polypropylene foam can be significantly improved when overcoming polypropylene expanded.
Description
Technical field
The present invention relates to technical field of macromolecules, more particularly to a kind of side by performed polymer expanded polypropylene foamed plastics
Method.
Background technology
Polypropylene material is to be most widely used in the world at present, and one of most fast general-purpose plastics of increase of production, it has
Relative density is small, wide material sources, be easily recycled, excellent in mechanical performance, high temperature resistant, corrosion-resistant, excellent electrical property, chemical stability
High, the features such as price is low, tasteless odorless, it is widely used in inner and outer decorative parts of automobile, electric equipment products and daily living article.
Since the 1970s, polypropylene foam product is progressively in automotive trim, packaging material, ornament materials, light containers etc.
Aspect is applied.Compared with general polystyrene foam at present, the shock resistance of polypropylene foam, recyclability are more
Good, compared with polyethylene, the intensity and heat resisting temperature of polypropylene foam are higher.At present, external a few countries such as U.S., moral
State and Italy etc. have been realized in the industrialized production of PP foamed plastics.In terms of China just starts PP foamed plastics in recent years
Research, technology is still immature so far, and industrialized production is also in the starting stage.
Foamed plastics is that gas is scattered in the aggregation formed in solid polymer, have it is light, heat-insulated, buffering, insulation,
Anti-corrosion, it is cheap the advantages that, therefore in commodity, packaging, industry, agricultural, transportation, war industry, aerospace industry
It is used widely.Current foamed plastics principal item has polystyrene（PS）, polyethylene（PE）, polyurethane (PUR).But by
In " white pollution " problem of polystyrene, the residue and cross-linked polyethylene foam of polyurethane foam foaming process use temperature
The presence for spending low problem limits using and developing for foamed plastics.Polypropylene foam, can because its temperature in use is high
Recycling, excellent mechanical property and chemicals-resistant, oil resistivity and it is heat-insulated the advantages that, PP foam material into
Heat-barrier material is buffered for fastest-rising environment-friendly novel resistance to compression at present.
EPP (Expanded Polypropylene) is expanded polypropylene material, and it is a kind of the highly crystalline of performance brilliance
Type polymer/gas recombination material, fastest-rising environment-friendly novel resistance to compression at present is turned into its unique and superior performance and buffered
Heat-barrier material.
EPP products have very excellent antidetonation energy absorption performance, response rate is high after deformation, good heat resistance, chemically-resistant
Product, oil resistivity and thermal insulation；Meanwhile its light weight, article quality can be greatly reduced；In addition, EPP or a kind of environmentally friendly material
Material, it is prone to which β degrades, and PP foams are easy to recycle, and its environment friendly is better than other foamed materials, thus is referred to as
" green " foam.The excellent properties showed just because of it so that EPP turns into after polystyrene (EPS), polyurethane
(EPU) novel foam material of application value and market potential, is had more after polyethylene (EPE) foamed material.
The PP of conventional method production is a kind of line style semicrystalline polymeric, and strand is seldom branched, molecular weight distribution phase
To narrower, this cause its softening point and fusing point very close to.Before temperature reaches fusing point, it does not flow substantially, when temperature surpasses
After crossing fusing point, melt strength drastically declines, and this melt is difficult to encase gas；In addition, polypropylene is changed into crystallization from molten state
State can release substantial amounts of heat, longer the time required to being solid by melt transform；In addition polypropylene air penetrability is high, and foamed gas are easy
Escape.Therefore it is narrow suitable for polypropylene expanded temperature range, foaming process is difficult control, easily causes steep that wall in foaming process to break
Split, gas is escaped, abscess caves in and bubble merges.The PP foam material technological means of high quality is obtained at present, is mainly enclosed
Around the melt strength for being raising PP, including the means such as grafting, cross-linking modified and blending and modifying.
The content of the invention
It is difficult control for current polypropylene expanded process, easily causes steep that wall rupture in foaming process, gas escape, bubble
The defects of hole caves in and bubble merges, it is an object of the invention to provide a kind of side by performed polymer expanded polypropylene foamed plastics
Method, it is easily controlled with reaction, and reaction condition is simple, and obtained polypropylene foam intensity it is high the characteristics of.
To solve the above problems, the present invention uses following technical scheme：
A kind of method by performed polymer expanded polypropylene foamed plastics, comprise the following steps：
（1）Propylene monomer and catalyst are well mixed in a solvent, prepolymerization is then carried out in a kettle, obtains third
Alkene performed polymer；
（2）Propylene performed polymer, propylene, foaming agent, catalyst and auxiliary agent are added in mould, pouring molding is carried out, obtains pre- production
Thing；
（3）Pre-product is foamed at 164 ~ 170 DEG C, obtains polypropylene foam.
In the present invention first under the conditions of existing for catalyst, propylene monomer is subjected to prepolymerization reaction in a solvent, then will
After performed polymer mixes with propylene monomer, extrusion molding at low temperature, the speed of control propylene foaming, the speed that propylene foams is reduced
Rate, and the operating procedure of the present invention is simple, without processes such as HTHPs, by the way that propylene monomer and propylene performed polymer is anti-
Should, it is possible to increase the intensity of polypropylene foam.
Catalyst can be catalyzed the prepolymerization reaction of propylene, it is preferred that the catalyst is Ziegler-Natta catalyst, metatitanic acid
Four isobutyl esters, at least one of stannous octoate or dibutyl tin laurate.
Organic solvent can improve the uniformity of material mixing, and the present invention does not have special want to the species of organic solvent
Ask, can be well known to the art personnel, in step as long as can play a part of and dissolve ultra-violet absorber
Suddenly（1）In, the solvent is acetone, DMF, 1-METHYLPYRROLIDONE, DMA, diformazan
Yl acetamide, dichloromethane, triethyl phosphate, acetone, chloroform, toluene, ethanol, acetic acid, ethyl acetate, formic acid, chloroform,
At least one of tetrahydrofuran, atoleine, water and dimethyl sulfoxide (DMSO).
An important factor for condition of prepolymerization reaction is control later stage polypropylene foam expansion rate, in order to reduce polypropylene bubble
The expansion rate of foam, it is preferred that in step（1）In, the temperature of the prepolymerization is 40 ~ 68 DEG C, and the time is 15 ~ 45min.
The mass ratio of propylene performed polymer and the propylene is an important factor for influenceing melt strength of polypropylene, it is preferred that
Step（2）In, the mass ratio of propylene performed polymer and the propylene is 1:（0.3~1.5）.
Initiator refers to the compound that can promote molecule chain extension, extend, and initiator can carry out polypropylene reaction system
Chain extension and crosslinking, they have the characteristic group that can be chemically reacted with reaction system, and molecular weight is low, and reaction is active, they
The reaction speed of reaction system can extremely efficient be adjusted.In step（2）In, the initiator be ethylene glycol, propane diols, Isosorbide-5-Nitrae-
Butanediol, diglycol, glycerine, trimethylolpropane, Isosorbide-5-Nitrae-cyclohexanediol, hydrogenated bisphenol A, α-glycerol allyl base
At least one of ether, glycidol allyl ether, cumyl peroxide, sulphur.
In step（2）In, the auxiliary agent is olefin polymer, nucleator, crosslinking agent, antioxidant, light stabilizer, antistatic
At least one of agent, fire retardant and colouring agent.
In above-mentioned auxiliary agent, nucleator be preferably talcum powder, citric acid, sodium carbonate, calcium carbonate, silica, montmorillonite,
One or more in kaolin and titanium dioxide.Antioxidant is preferably one kind or several in antioxidant B215,2215,1010
Kind.Light stabilizer is preferably carbon black, zinc oxide, titanium dioxide, benzophenone, salicylic acid, benzotriazole, hindered amine
One or more in analog derivative.Antistatic additive can be that cationic antistatic agent, anionic antistatic agents or nonionic resist
Electrostatic agent such as ethoxylated fat race alkylamine.
To adjust expanded polypropylene product pliability, the present invention further preferably adds other olefin polymers, institute into raw material
State other olefin polymers to refer to remove the olefin polymer outside polypropylene, the olefin polymer of addition is preferably that low-density is gathered
Ethene (LDPE), high density polyethylene (HDPE) (HDPE), LLDPE (LLDPE), metallocene linear-low density polyethylene
(mLLDPE), ethylene-vinyl acetate copolymer (EVA), polyolefin elastomer (POE), styrene butadiene styrene block copolymerization
One or more in thing (SBS), ethylene propylene diene rubber (EPDM).Those skilled in the art can be according to the performance of expected product
Select specific olefin polymer type.
A kind of method by performed polymer expanded polypropylene foam of the invention, compared with prior art, the characteristics of it is protruded and
Excellent effect is：
In the present invention first under the conditions of existing for catalyst, propylene monomer is subjected to prepolymerization reaction in a solvent, then by pre-polymerization
After body mixes with propylene monomer, extrusion molding at low temperature, the speed of control propylene foaming, the speed that propylene foams is reduced, and
And the operating procedure of the present invention is simple, without processes such as HTHPs, by by propylene monomer and propylene prepolymer reaction, gathering
Close and foamed in course of reaction, it is possible to increase polypropylene foam melt strength.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of method by performed polymer expanded polypropylene foam, comprise the following steps：
（1）Propylene monomer and Ziegler-Natta catalyst are well mixed in triethyl phosphate, then carried out in a kettle
Prepolymerization, the temperature of the prepolymerization is 40 DEG C, time 15min, obtains propylene performed polymer；
（2）It is by the mass ratio that propylene performed polymer is pressed with the propylene（1:0.3）, foaming agent, Ziegler-Natta catalyst and alkene
Hydrocarbon polymer is added in mould, is carried out pouring molding, is obtained pre-product；
（3）Pre-product is foamed at 164 DEG C, obtains polypropylene foam.
Embodiment 2
A kind of method by performed polymer expanded polypropylene foam, comprise the following steps：
（1）Propylene monomer and tetrabutyl titanate are well mixed in triethyl phosphate, then carry out pre-polymerization in a kettle
Reaction is closed, the temperature of the prepolymerization is 45 DEG C, time 25min, obtains propylene performed polymer；
（2）It is by the mass ratio that propylene performed polymer is pressed with the propylene（1:0.4）Foaming agent, tetrabutyl titanate and olefinic polymerization
Thing is added in mould, is carried out pouring molding, is obtained pre-product；
（3）Pre-product is foamed at 165 DEG C, obtains polypropylene foam.
Embodiment 3
A kind of method by performed polymer expanded polypropylene foam, comprise the following steps：
（1）Propylene monomer and tetrabutyl titanate are well mixed in acetone, then carry out prepolymerization in a kettle,
The temperature of the prepolymerization is 50 DEG C, time 20min, obtains propylene performed polymer；
（2）It is by the mass ratio that propylene performed polymer is pressed with the propylene（1:0.5）, foaming agent, tetrabutyl titanate and metallocene
LLDPE (mLLDPE) is added in mould, is carried out pouring molding, is obtained pre-product；
（3）Pre-product is foamed at 168 DEG C, obtains polypropylene foam.
Embodiment 4
A kind of method by performed polymer expanded polypropylene foam, comprise the following steps：
（1）Propylene monomer and dibutyl tin laurate are well mixed in chloroform, then carried out in a kettle pre-
Polymerisation, the temperature of the prepolymerization is 50 DEG C, time 30min, obtains propylene performed polymer；
（2）It is by the mass ratio that propylene performed polymer is pressed with the propylene（1:1）, foaming agent, dibutyl tin laurate and cyclopentadienyl gold
Belong to LLDPE (mLLDPE) to add in mould, carry out pouring molding, obtain pre-product；
（3）Pre-product is foamed at 169 DEG C, obtains polypropylene foam.
Embodiment 5
A kind of method by performed polymer expanded polypropylene foam, comprise the following steps：
（1）Propylene monomer and Ziegler-Natta catalyst are well mixed in acetone, then carry out prepolymerization in a kettle
Reaction, the temperature of the prepolymerization is 58 DEG C, time 44min, obtains propylene performed polymer；
（2）It is by the mass ratio that propylene performed polymer is pressed with the propylene（1:1.2）, foaming agent, Ziegler-Natta catalyst and second
Alkene acetate ethylene copolymer (EVA) is added in mould, is carried out pouring molding, is obtained pre-product；
（3）Pre-product is foamed at 169 DEG C, obtains polypropylene foam.
Comparative example 1
A kind of method by performed polymer expanded polypropylene foam, comprise the following steps：
（1）Propylene monomer and Ziegler-Natta catalyst are well mixed in triethyl phosphate, then carried out in a kettle
Prepolymerization, the temperature of the prepolymerization is 40 DEG C, time 15min, obtains propylene performed polymer；
（2）Propylene performed polymer, foaming agent, Ziegler-Natta catalyst and olefin polymer are added in mould, pour building up
Type, obtain pre-product；
（3）Pre-product is foamed at 164 DEG C, obtains polypropylene foam.
Comparative example 2
A kind of method by performed polymer expanded polypropylene foam, comprise the following steps：
（1）Propylene monomer and Ziegler-Natta catalyst are well mixed in triethyl phosphate, then carried out in a kettle
Prepolymerization, the temperature of the prepolymerization is 40 DEG C, time 15min, obtains propylene performed polymer；
（2）It is by the mass ratio that propylene performed polymer is pressed with the propylene（1:0.3）, foaming agent, olefin polymer add mould in,
Pouring molding is carried out, obtains pre-product；
（3）Pre-product is foamed at 184 DEG C, obtains polypropylene foam.
Test：
The expansion ratio and shrinkage factor of carbon dioxide-base biodegradable foam obtained above are detected.Wherein, foam
Multiplying power is tested using foamed plastics rubber pange multiplying power tester；Shrinkage factor is according to DIN ISO 2796 in 60 DEG C, 4 hours conditions
Lower detection), experimental result is as shown in table 1.
Table 1
From analysis of experimental results, cancellation propylene still cancels catalyst either in pre-polymerization mould, reduces polymerization
One of foaming mechanism simultaneously so that the foam performance of final polypropylene foam substantially reduces.
Claims (8)
- A kind of 1. method by performed polymer expanded polypropylene foamed plastics, it is characterised in that comprise the following steps：（1）Propylene monomer and catalyst are well mixed in a solvent, prepolymerization is then carried out in a kettle, obtains third Alkene performed polymer；（2）Propylene performed polymer, propylene, foaming agent, catalyst and auxiliary agent are added in mould, pouring molding is carried out, obtains pre- production Thing；（3）Prepolymer is foamed at 164 ~ 170 DEG C, obtains polypropylene foam.
- 2. the method according to claim 1 by performed polymer expanded polypropylene foamed plastics, it is characterised in that in step （1）In, the catalyst is Ziegler-Natta catalyst, tetrabutyl titanate, stannous octoate or dibutyl tin laurate etc. At least one of.
- 3. the method according to claim 2 by performed polymer expanded polypropylene foamed plastics, it is characterised in that in step （1）In, the solvent is acetone, DMF, 1-METHYLPYRROLIDONE, DMA, dimethyl Acetamide, dichloromethane, triethyl phosphate, acetone, chloroform, toluene, ethanol, acetic acid, ethyl acetate, formic acid, chloroform, four At least one of hydrogen furans, atoleine, water and dimethyl sulfoxide (DMSO).
- 4. the method according to claim 3 by performed polymer expanded polypropylene foamed plastics, it is characterised in that in step （1）In, the temperature of the prepolymerization is 40 ~ 68 DEG C, and the time is 15 ~ 45min.
- 5. the method according to claim 1 by performed polymer expanded polypropylene foamed plastics, it is characterised in that in step （2）In, the mass ratio of propylene performed polymer and the propylene is 1:（0.3~1.5）.
- 6. the method according to claim 1 by performed polymer expanded polypropylene foamed plastics, it is characterised in that in step （2）In, the initiator be ethylene glycol, propane diols, BDO, diglycol, glycerine, trimethylolpropane, In Isosorbide-5-Nitrae-cyclohexanediol, hydrogenated bisphenol A, α-allylin, glycidol allyl ether, cumyl peroxide, sulphur At least one.
- 7. the method according to claim 6 by performed polymer expanded polypropylene foamed plastics, it is characterised in that in step （2）In, in step（2）In, the auxiliary agent be nucleator, crosslinking agent, antioxidant, light stabilizer, antistatic additive, fire retardant and At least one of toner.
- 8. the method by performed polymer expanded polypropylene foamed plastics according to any one in claim 1 ~ 7, its feature It is, the nucleator is talcum powder, citric acid, sodium carbonate, calcium carbonate, silica, montmorillonite, kaolin and titanium dioxide At least one of；And/orThe antioxidant is antioxidant B215,2215, at least one of 1010；And/orThe light stabilizer is carbon black, zinc oxide, titanium dioxide, benzophenone, salicylic acid, benzotriazole, hindered amine At least one of analog derivative；And/orThe antistatic additive ethoxylated fat race alkylamine.
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| CN201710705951.2A CN107522891A (en) | 2017-08-17 | 2017-08-17 | A kind of method by performed polymer expanded polypropylene foamed plastics |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081914A (en) * | 2007-07-06 | 2007-12-05 | 天津市润生塑胶制品有限公司 | Polypropylene expanded material and method for manufacturing same |
| CN102250423A (en) * | 2011-07-08 | 2011-11-23 | 中国石油化工股份有限公司 | Foaming polypropylene composition |
| CN102504325A (en) * | 2011-11-18 | 2012-06-20 | 中国科学院长春应用化学研究所 | Preparation method for foamed polypropylene |
-
2017
- 2017-08-17 CN CN201710705951.2A patent/CN107522891A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081914A (en) * | 2007-07-06 | 2007-12-05 | 天津市润生塑胶制品有限公司 | Polypropylene expanded material and method for manufacturing same |
| CN102250423A (en) * | 2011-07-08 | 2011-11-23 | 中国石油化工股份有限公司 | Foaming polypropylene composition |
| CN102504325A (en) * | 2011-11-18 | 2012-06-20 | 中国科学院长春应用化学研究所 | Preparation method for foamed polypropylene |
Non-Patent Citations (2)
| Title |
|---|
| 复旦大学高分子科学系 编著: "《高分子化学》", 31 December 1995, 复旦大学出版社 * |
| 韦军主编: "《高分子合成工艺学》", 31 December 2011 * |
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Application publication date: 20171229 |