CN1173001C - Adhesive resin composition - Google Patents
Adhesive resin composition Download PDFInfo
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- CN1173001C CN1173001C CNB011311347A CN01131134A CN1173001C CN 1173001 C CN1173001 C CN 1173001C CN B011311347 A CNB011311347 A CN B011311347A CN 01131134 A CN01131134 A CN 01131134A CN 1173001 C CN1173001 C CN 1173001C
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- adhesive resin
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Abstract
The present invention provides an adhesive resin composition which is a mixture formed by grafting polyethylene to linear low-density polyethylene, polypropylene, polystyrene, POE(the copolymerization of ethene and propene in the proportion of 1 to 1), etc. Resin has excellent adhesion to aluminum / plastic materials (the peeling strength is larger than 100N/25mm), the physical property achieves the continuous industrial production requirement of an aluminum-plastic compound tube, and the resin also has excellent adhesion to PE, PP, EVA, nylon, PVOH, polyamide, polycarbonate, metal (such as steel, iron, copper, etc.), leather, timber, paper, glass fiber, etc. The adhesive resin composition is suitable for industrial application.
Description
The present invention relates to a kind of polyolefine resin composition, be specifically related to a kind of close-burning polyolefine resin composition that has, the interlayer that is specially adapted to aluminum-plastic laminated tube is compound.
Plastic-aluminum combined effective tackifying resin uses as aluminium/plastics interlayer adhesive in the manufacturing of aluminum-plastic laminated tube, and it and aluminium have good binding property, with plastics good consistency are arranged again.The production of aluminum-plastic laminated tube is continuous extrusion simultaneously, and the physicals of tackifying resin should satisfy the requirement of extruding continuously.
US patent 4,409,364 disclose a kind of prescription of resin of binding property, mainly are made up of the grafted polyethylene of 0.1～40wt% and the blending resin of 60～99.9wt%, and this blending resin is made up of the high density polyethylene(HDPE) (HDPE) of 25～90wt% and the polypropylene (PP) of 10～75wt%.To have adopted the copolymerization HDPE of the following ethylenic unsaturation hydro carbons of ethylene homo or eight carbon atoms be base-material to grafts in the patented technology, has at initiator with the grafted monomer that contains one or more unsaturated carboxylic acids or acid anhydrides that reaction makes in the Brabender mixing tank.For the binding property that improves grafting HDPE copolymerization PP, HDPE and the grafting HDPE of ethylene homo or eight ethylenic unsaturation hydro carbons below the carbon atom carried out blending, the tackifying resin of gained has binding property preferably.Can be used for compound two-layer or multilayer is of the same race or polarity, non-polar material not of the same race.Tackifying resin of enumerating in the patent and the maximum peeling strength of EVA are 7.8 pounds/inch; With the maximum peeling strength of PP be 7.1 pounds/inch; With the maximum peeling strength of nylon 6 be 4.6 pounds of/inch (ASTMD 1876-72 standard testing, 1 pounds/inch=4.5N/25mm).
US patent 4,452,942 also discloses a kind of prescription of tackifying resin, mainly form by the grafted polyethylene of 0.1～95wt% and the blending resin of 99.9～5wt%, this blending resin can be polyethylene, ethene,
aThe multipolymer of the unsaturated ester of-ethylene copolymer or ethene and vinyl.This patent is that the grafted monomer with linear low density polyethylene (LLDPE) and one or more unsaturated carboxylic acid or acid anhydrides carries out grafting in the presence of initiator.Reduced the tack temperature of grafting HDPE, and the binding property of grafting LLDPE is similar to grafting HDPE.Preparation grafting LLDPE processing unit preferably uses twin screw extruder.Tackifying resin of enumerating in the patent and the maximum peeling strength of aluminium foil＞7.0 pound/inch; With the maximum peeling strength of EVA be 6.3 pounds/inch; The stripping strength of nylon 6＞7.9 pound/inch; Reach 3.2 pounds/inch with the stripping strength of EVOH; Reach 1.7 pounds/inch with the stripping strength of PE; But with acrylonitrile-butadiene blend film tight bond; Reach not peelable (according to ASTMD 1876-78 standard testing) with paper is bonding.
" synthetic resins and plastics " (Vol.12 No.4 1995) " polycthylene grafted modification and with the cohesiveness of aluminium " be with polyethylene in the presence of peroxidation two propyl benzene respectively with molten monomers such as vinylformic acid, MALEIC ANHYDRIDE, maleic acid sodium, vinylformic acid carboxylic propyl ester, glytidyl methacrylate extrude, the infrared spectra of product show polyethylene in various degree connected various polar groups.Between the aluminium foil of two-layer 25.4mm, put the grafted polyethylene sample on hydropress at 200 ℃ of following pressurized 2MPa.Stripping test is carried out peeling off for 180 ° by the ASTM-D903 work on DL-1000B type electronic tensile machine, and speed is 200mm/min.Wherein the high-peeling strength of the stripping strength of the polyethylene of acid anhydrides functionalization and aluminium can reach 980N/m.The cohesiveness that replaces polyethylene and aluminium with EVA further raising can reach 620N/m through the high-peeling strength of 65 ℃ hot-water soak 12h.
" Chinese tackiness agent " (Vol.5 No.4 1995) " tackifying resin with the research of grafted polyethylene " literary composition is to be matrix polymer with the polyethylene, with the maleic anhydride is that monomer carries out graft reaction, studied proportioning raw materials, initiator amount, factor such as temperature of reaction and time is to the influence of percentage of grafting, inquired into the possibility that this grafts is made the base polymer of tackifying resin.
" chemistry is with bonding " (No.1 1999) " bonding research of polyethylene and aluminium " is by the selection of the modification of polyethylene body, surface modification and tackiness agent, inquired into the bonding of polyethylene and aluminium, find to make aluminium and polyethylene reach good bonding stripping strength maximum and can reach 30N/cm by surface modification or the modification of use body.
We find test by repeatedly, the melt flow rate (MFR) of grafted polyethylene of the prior art is lower, mechanical property is relatively poor, can not satisfy the standard (stripping strength＞100N/25mm (GB2791-81) of domestic production of aluminum industry, elongation at break＞400% (GB1040-90), melt flow rate (MFR)＞2.0g/10min (GB3682-89)).There is not the concrete physical performance index of tackifying resin in the prior art document as a reference yet.
The purpose of this invention is to provide the resin combination that a kind of physicals and viscosity all satisfy the processing request of aluminum-plastic laminated tube.
Resin combination of the present invention is that the blending resin by the grafted polyethylene of 0.1～90wt% and 10～99.9wt% carries out blending and makes in twin screw extruder.Wherein blending temperature is 170 ℃～240 ℃, screw speed is 30～100 rev/mins, and blending resin comprises: the LLDPE of 5～98wt%, the PP of 1～55wt%, 0.5 the POE of～20wt% (ethene, propylene were with copolymerization in 1: 1), the polystyrene of 0.5～20wt% (PS).The oxidation inhibitor that can also add 1 ‰～10wt% as required in the resin.
Grafted polyethylene is HDPE fusion-grafting thing in the presence of peroxide initiator of unsaturated carboxylic acid, acid anhydrides or carboxylicesters and ethylene homo or unsaturated olefin copolymerization, reaction can be carried out in twin screw extruder or Brabender pony mixer, processing temperature is 150 ℃～190 ℃, reaction times 5～7min.The peroxide initiator that is used to react does not have special requirement, and its transformation period and temperature of reaction are complementary and get final product, and commonly used is dicumyl peroxide.Unsaturated carboxylic acid, acid anhydrides or carboxylicesters can have following selection: vinylformic acid, methacrylic acid, maleic acid, 2-methylene-succinic acid, citraconic acid, methyl 2-butylene diacid, MALEIC ANHYDRIDE, 4-methyl-4-tetrahydrobenzene-1,2 dicarboxylic anhydride diolefine maleate, diolefine trans-succinate ester, diolefine 2-methylene radical fourth diester, diolefine are along methyl butene diester, methacrylic ester, alkylmethacrylate, vinylformic acid carboxylic propyl ester etc.The most frequently used is MALEIC ANHYDRIDE.
Compare with other graft polyolefins such as grafting LDPE, grafting EVA, the cohesiveness of grafting HDPE and polar material is lower.The PP that adds ethylene homo or unsaturated olefin copolymerization significantly improves the stripping strength of grafting HDPE, and its reason is still waiting research.
Add the tensile strength that LLDPE can improve material in the resin.Short and small side chain around the main chain of LLDPE can make between LLDPE and HDPE grafts, PP and form hydrogen bond and the Van der Waals force that is evenly distributed, and mixes more even; The long-chain of LLDPE makes resin have good elongation, tear resistance again, has reduced the bonding temperature of fusion of resin.
Aluminum-plastic laminated tube is to extrude production process continuously, this needs tackifying resin to have certain melt flow rate (MFR), the grafted chain of grafting HDPE and the linear backbone of LLDPE make blending resin form the structure of similar network, the melt flow rate (MFR) of resin is lower, and that can not satisfy aluminum-plastic laminated tube extrudes the production needs continuously.Test finds to add the fluidity of molten that rigid material PS can obviously improve resin.Think that PS and polyolefinic consistency are very poor, the PS of adding forms " obstruct " to long-chain in system, destroyed network structure, and " molecular weight " of having widened material distributes, and improved the melt flow rate (MFR) of tackifying resin.
The adding of PS descends the toughness of resin.POE (ethylene propylene copolymer) is as a kind of thermoplastic elastomer, and it forms less one the rubber areas of relatively advising in PP, and is evenly distributed in the tackifying resin intermingling material with PP.Improved the toughness of material.
Stripping strength＞the 100N/25mm of tackifying resin composition of the present invention (GB2791-81), every physicals satisfies the industrial production of aluminum-plastic laminated tube fully.Also show good cohesiveness with materials such as metals such as PE, PP, EVA, nylon, PVOH, polymeric amide, polycarbonate, steel, iron, copper, leather, timber, paper, glass fibre.
Comparative Examples 1:
With the dicumyl peroxide is initiator, is 5.8g/10min with melt flow rate (MFR) (MFR), and density p is 0.968g/cm
3HDPE and MALEIC ANHYDRIDE 150 ℃～190 ℃ following reaction 6min in the response type forcing machine of Φ 48; Obtain HDPE grafts (HDPE-g-MAH).Be 5.8g/10min with grafts and melt flow rate (MFR) (MFR) again, density (ρ) is 0.968g/cm
3HDPE in 170～240 ℃ of following twin screw extruders, carry out blending with 1: 4 (weight ratio), obtain tackifying resin.
The tackifying resin for preparing is carried out mechanical test.(test result sees Table 1 for 50mm * 120mm) 235 ℃ of temperature, compound 5min under the 6kg pressure, table 2 with aluminium foil again.
Embodiment 1:
Make HDPE-g-MAH with Comparative Examples 1 same method, and in twin screw extruder, carry out blending under 170～240 ℃ the temperature by following proportioning (parts by weight).
HDPE-g-MAH 20
LLDPE (MFR1.0，ρ0.925) 50
PP (MFR28，ρ0.902) 20
POE (MFR0.5～30，ρ0.864～0.880) 5
PS (MFR7.0) 5
The tackifying resin that makes is tested, and test condition and Comparative Examples 1 the results are shown in Table 1 together
Embodiment 2:
The HDPE-g-MAH of preparation in the Comparative Examples 1 is carried out blending by following proportioning (parts by weight) under same processing condition.
HDPE-g-MAH 50
LLDPE (MFR1.9，ρ0.925) 35
PP (MFR28，ρ0.902) 10
POE (MFR0.5～30，ρ0.864～0.880) 2
PS (MFR7.0) 3
Product is tested according to the testing method of Comparative Examples 1 and is tested, and test result sees Table 1.
Embodiment 3:
The HDPE-g-MAH of preparation in the Comparative Examples 1 is carried out blending by following proportioning (parts by weight) in same processing condition.
HDPE-g-MAH 90
LLDPE (MFR1.9，ρ0.925) 8
PP (MFR28，ρ0.902) 1
POE (MFR0.5～30，ρ0.864～0.880) 0.5
PS (MFR7.0) 0.5
Product is tested according to the testing method of Comparative Examples 1 and is tested, and test result sees Table 1.
Embodiment 4
With the dicumyl peroxide is initiator, is 5.8g/10min with melt flow rate (MFR) (MFR), and density p is 0.968g/cm
3HDPE and vinylformic acid 150 ℃～190 ℃ following reaction 6min in the response type forcing machine of Φ 48; Obtain HDPE grafts (HDPE-g-AA).Again grafts is carried out blending by the mixing proportion of embodiment 1, obtain tackifying resin.(test result sees Table 1 for 50mm * 120mm) 235 ℃ of temperature, compound 5min under the 6kg pressure with aluminium foil again.
Table 1 tackifying resin testing experiment result
| Project | Melt flow rate (MFR) g/10mm | Tensile strength MPa | Elongation at break % | Stripping strength N/25mm (with aluminium) |
| (GB3682-89) | (GB1040-90) | (GB2791-81) | ||
| Comparative Examples 1 | 0.66 | 12.4 | 140 | 66.9 |
| Embodiment 1 | 3.2 | 23.75 | 664 | 189 |
| Embodiment 2 | 2.8 | 14.7 | 560 | 129.4 |
| Embodiment 3 | 2.3 | 12.9 | 420 | 103 |
| Embodiment 4 | - | - | - | 120 |
The cohesiveness of table 2 embodiment 1 preparation tackifying resin and material
| Project | Stripping strength N/25mm |
| Resin/eva film (VA content 5%) | Not peelable |
| Resin/eva film (VA content 14%) | Not peelable |
| Resin/eva film (VA content 28%) | Not peelable |
| Resin/nylon 6 films | Not peelable |
| Resin/polyethylene film | Not peelable |
| Resin/polypropylene film | Not peelable |
| Resin/steel band- | 200 |
Complex method and tackifying resin/aluminium foil are together
Claims (6)
1. adhesive resin composition, form by the grafted polyethylene of 0.1～90wt% and the blending resin of 10～99.9wt%, the linear low density polyethylene that it is characterized in that consisting of of blending resin: 5～98wt%, the polypropylene of 1～55wt%, 0.5 the ethene of～20wt%, propylene copolymer, the polystyrene of 0.5～20wt%.
2. adhesive resin composition according to claim 1 is characterized in that the mass percent of ethene and propylene is 1: 1 in ethene, the propylene copolymer.
3. adhesive resin composition according to claim 1 is characterized in that the copolymer comprised 0.5～5wt% of ethene in the blending resin, propylene, and polystyrene accounts for 0.5～5wt%.
4. adhesive resin composition according to claim 1 is characterized in that grafted polyethylene is the fusion-grafting thing of high density polyethylene(HDPE) in the presence of peroxide initiator of unsaturated carboxylic acid, acid anhydrides or carboxylicesters and ethylene homo or unsaturated olefin copolymerization.
5. adhesive resin composition according to claim 1 is characterized in that grafted polyethylene is the fusion-grafting thing of MALEIC ANHYDRIDE and high density polyethylene(HDPE).
6. adhesive resin composition according to claim 1 is characterized in that grafted polyethylene is the fusion-grafting thing of vinylformic acid and high density polyethylene(HDPE).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011311347A CN1173001C (en) | 2001-09-03 | 2001-09-03 | Adhesive resin composition |
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|---|---|---|---|
| CNB011311347A CN1173001C (en) | 2001-09-03 | 2001-09-03 | Adhesive resin composition |
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| CN1403521A CN1403521A (en) | 2003-03-19 |
| CN1173001C true CN1173001C (en) | 2004-10-27 |
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| CNB011311347A Expired - Fee Related CN1173001C (en) | 2001-09-03 | 2001-09-03 | Adhesive resin composition |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602005021222D1 (en) * | 2004-06-28 | 2010-06-24 | Dow Global Technologies Inc | ADHESIVE AMPLIFIER FOR MULTILAYER LAMINATES |
| ATE426637T1 (en) * | 2004-12-16 | 2009-04-15 | Saudi Basic Ind Corp | POLYPROPYLENE COMPOSITION WITH IMPROVED SCRATCH RESISTANCE |
| CN102705691B (en) * | 2012-06-29 | 2015-04-15 | 宁夏青龙塑料管材有限公司 | Reinforced polyethylene composite pipe with oil resistance and organic solvent corrosion resistance |
| CN103374820A (en) * | 2013-07-26 | 2013-10-30 | 浙江鹏远新材料有限公司 | Antiskid woven cloth and preparation method thereof |
| CN110157355A (en) * | 2018-03-26 | 2019-08-23 | 广州市伟旺热熔胶科技有限公司 | A kind of high-temperature-resistance polyolefin hot melt adhesive and preparation method thereof |
| CN109401643A (en) * | 2018-09-30 | 2019-03-01 | 金旸（厦门）新材料科技有限公司 | One kind having high bonding force steel band reinforced polyethylene spiral ripple pipe special bonding resin material and preparation method thereof |
| CN113278392B (en) * | 2021-05-17 | 2023-02-03 | 山东东宏管业股份有限公司 | Steel wire pipe bonding resin and preparation method and application thereof |
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