CN110317352B - Preparation method of polarity-enhanced and flexible tackified polyolefin stainless steel waterproof composite belt - Google Patents
Preparation method of polarity-enhanced and flexible tackified polyolefin stainless steel waterproof composite belt Download PDFInfo
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- CN110317352B CN110317352B CN201910502028.8A CN201910502028A CN110317352B CN 110317352 B CN110317352 B CN 110317352B CN 201910502028 A CN201910502028 A CN 201910502028A CN 110317352 B CN110317352 B CN 110317352B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D29/00—Producing belts or bands
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/121—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives by heating
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- 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
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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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/16—Homopolymers or copolymers of alkyl-substituted styrenes
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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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Abstract
The invention provides a preparation method of a polarity-enhanced and flexible tackified polyolefin stainless steel waterproof composite belt5-g-MAH, PAMS; and then, carrying out hot bonding on the obtained plastic base material and a stainless steel metal base material to obtain the stainless steel/plastic composite belt with high bonding strength and soaking resistance in hot water. PAMS and C5The simultaneous addition of the g-MAH can increase the bonding sites of the modified blend, strengthen the movement capability of molecular chain segments and increase the effective bonding of the modified film to the stainless steel in a molten state, thereby increasing the peel strength between the modified film and the stainless steel.
Description
Technical Field
The invention relates to the field of communication material manufacturing, in particular to a preparation and bonding method of a bonding layer resin for a steel-plastic composite belt with stronger hot water resistance.
Background
In the field of communication, optical fiber cables are required to be used as transmission carriers for signal transmission, and the performance of the metal/plastic composite tape has an important influence on the stability of optical fiber signal transmission and the service life of optical fibers. The metal/plastic composite tape is a laminated structure in which plastic and metal are integrally bonded to each other at normal temperature or under heating. The polarity of the metal surface is very strong, the polarity of the polyolefin resin surface is very weak, the adhesive strength of the metal surface and the polyolefin resin surface is low after the metal surface and the polyolefin resin surface are subjected to heat laminating treatment to form a composite belt, and blending modification of the polyolefin resin and the resin with the polarity is a common method for solving the problem of low adhesive strength of the composite belt. The common metal/plastic composite belt mostly adopts an aluminum-plastic composite belt, the common aluminum surface is easy to generate oxidation reaction, ethylene vinyl acetate copolymer (EVA) with better compatibility is only added into plastic polyolefin to improve the polarity, and the common aluminum-plastic composite belt can be prepared by hot press molding. The traditional aluminum-plastic composite belt can be applied to most environments, and some special environments are not suitable for the aluminum-plastic composite belt, such as severe environments of submarine cables, frozen soil and the like. Stainless steel is the first choice for preparing the composite strip metal substrate in the severe environments due to excellent mechanical property, corrosion resistance and lower price. Therefore, the stainless steel-plastic composite tape is required to be used as a protective shielding layer of the optical cable, but the stainless steel is difficult to be bonded by common adhesive resin such as EVA (ethylene vinyl acetate copolymer) and the like, and particularly the peel strength of the stainless steel-plastic composite tape after being soaked in water is very low and is difficult to reach the peel strength (the peel strength is more than or equal to 6.18N/cm) after being soaked in water at 68 ℃ for 168 hours of the industry standard YD/T723.2-2007. The existing stainless steel is generally bonded by adopting a thermosetting glue water mode of surface crosslinking, but the thermosetting glue water can not be subjected to secondary melting processing, and the process condition of producing the cable by using the metal/plastic composite belt is limited. The stainless steel surface coating as reported in publication No. CN104371533A, comprises, by mass, 10-30% of high-functional group urethane acrylate, 5-8% of fluorine-containing resin, 5-10% of epoxy resin, 1-5% of nano silica, 10-25% of an auxiliary agent, and the balance of water. The stainless steel surface coating prepared by the method has better chemical stability and can be attached to the surface of stainless steel for a long time, but the method also has the defects of incapability of realizing continuous production, low preparation efficiency, low yield, difficulty in secondary forming processing of thermosetting resin application and the like.
The technical scheme of the halogen-free flame-retardant metal composite belt reported by CN105799265A is that an acrylic acid adhesive: curing agent: dye: butanone: the mass ratio of toluene is 8-65: 0.003-0.02: 0-2: 3-27: 13-19, and finally preparing the high-molecular adhesive film. The macromolecule bonding layer prepared by the invention can obviously improve the peeling strength of the stainless steel plastic composite belt in the wire and cable. The proposal leads the adhesive layer and the stainless steel layer to generate stronger hydrogen bond acting force so as to improve the peeling strength. Butanone and toluene in the halogen-free flame-retardant adhesive resin prepared by the method are toxic, and the preparation process is easy to cause harm to operators. On the other hand, although the hydrogen bond can obviously improve the bonding acting force of the plastic and the stainless steel in a normal state, the water has strong polarity, and easily permeates into the adhesive layer and the stainless steel under the condition of heating to open the hydrogen bond, so that the peeling strength of the stainless steel/plastic composite belt is obviously reduced.
CN103895161A reports a preparation method of a stainless steel resin complex and a stainless steel resin complex prepared by the same, the technical proposal is that a stainless steel substrate after pretreatment is put into corrosive liquid for electrochemical corrosion, the corrosive liquid is ferric chloride solution with the mass concentration of 2-25 wt% and/or 5-35 wt%, then a resin composition is injected on the surface of the stainless steel substrate after corrosion treatment, and the stainless steel resin complex is obtained after molding.
Therefore, it is necessary to develop a stainless steel/blown film composite tape which has high bonding strength, is resistant to hot water immersion, is environment-friendly and is beneficial to continuous production.
Disclosure of Invention
The invention aims to solve the technical problems and provides a method for producing an environment-friendly metal/blown film composite belt with excellent hot water resistance.
The technical scheme of the invention can be realized by the following technical measures:
a preparation method of a polarity-enhanced and flexible tackified polyolefin stainless steel waterproof composite belt comprises the following steps:
preparing a plastic film substrate, wherein the raw materials of the plastic film substrate comprise EAA/EVA, LLDPE and C5-g-MAH, PAMS (poly alpha methyl styrene);
and (2) carrying out hot bonding on the plastic base material obtained in the step (1) and a stainless steel metal base material to obtain the stainless steel/plastic composite belt with high bonding strength and capable of being soaked in hot water.
Preferably, the plastic film substrate comprises the following components:
preferably, the plastic film substrate comprises the following components:
preferably, in the step (1), the plastic base material is extruded and granulated by a double screw and then blown into a film by a single screw.
Adding the materials into a parallel double-screw extruder for melt blending granulation, wherein the temperature of each part of the double-screw extruder is respectively set as follows: 175-180 ℃ in the first area, 180-185 ℃ in the second area, 190-195 ℃ in the third area, 200-205 ℃ in the fourth area, 190-195 ℃ in the fifth area, 185-190 ℃ in the machine head, 190-195 ℃ in the melt temperature and 35r/min in the screw rotation speed.
Adding the granulated resin into a single-screw extruder, wherein the temperature of each part of the single-screw extruder is respectively set as follows: 140-160 ℃ in the first area, 150-170 ℃ in the second area, 170-185 ℃ in the third area, 170-170 ℃ in the head, 145 ℃ in the mold temperature and 35r/min in the screw rotation speed. The extruded melt directly enters a die to be blown into a film.
Preferably, the LLDPE has a melt index of 1.6-2.6g/10 min. Further preferably, the LLDPE is 35B, the EAA is CS-1, and the AA content in the EAA is 14-40%. Said C5The melting point of the-g-MAH is 95 ℃ and the PAMS brand is Kristalex 3085.
Preferably, the hot bonding time of the stainless steel substrate and the plastic substrate in the step (2) is 0.5s-1s, the temperature is 170-180 ℃, and the pressure is 5kPa-6 kPa.
Preferably, the stainless steel may be replaced with other metals such as aluminum alloy or copper.
The polymer molecular chains of plastics generally have the characteristic that the flexibility is reduced when the polarity is enhanced, the two contradictory factors have great influence on the preparation of the stainless steel plastic composite belt, in order to improve the bonding capability of plastic polyolefin and stainless steel, the polarity of polyolefin needs to be further improved, but the improvement of the polarity causes the flexibility reduction of the molecular chain segments, and further influences the bonding strength of the composite belt. The invention utilizes PAMS and C5The g-MAH has the characteristics of low molecular weight, high flexibility and good compatibility with the aliphatic resin of EAA, EVA and LLDPE, is compounded with EAA/LLDPE or EVA/LLDPE, so that the molecular chain segment of the modified resin has more adhesive points while the activity of the molecular chain segment is greatly improved, the effective adhesion of the modified film to the stainless steel interface is improved, good interface contact with the stainless steel is obtained, the processability of the blend is improved, the energy consumption in the extrusion process is reduced due to the good processability, and the economic cost is reduced.
Drawings
The invention is further illustrated by means of the attached drawings, the examples of which are not to be construed as limiting the invention in any way.
FIG. 1 is a schematic representation of the bonding of a blended modified film of the present invention to stainless steel, wherein FIG. 1a is the bonding of a blend of EAA/EVA and LLDPE to stainless steel; FIG. 1b shows the case of using C5-g-MAH and PAMS to stainless steel.
Detailed Description
In order that the invention may be more readily understood, specific embodiments thereof will be described further below.
The adhesive layer resin of the present invention was prepared as follows:
the raw materials are weighed according to the proportion and added into a high-speed stirrer to be uniformly mixed at high speed.
Adding the materials into a parallel double-screw extruder for melt blending granulation, wherein the temperature of each part of the double-screw extruder is respectively set as follows: 175-180 ℃ in the first area, 180-185 ℃ in the second area, 190-195 ℃ in the third area, 200-205 ℃ in the fourth area, 190-195 ℃ in the fifth area, 185-190 ℃ in the machine head, 190-195 ℃ in the melt temperature and 35r/min in the screw rotation speed.
Adding the granulated resin into a single-screw extruder, wherein the temperature of each part of the single-screw extruder is respectively set as follows: 140-160 ℃ in the first area, 150-170 ℃ in the second area, 170-185 ℃ in the third area, 170-170 ℃ in the head, 145 ℃ in the mold temperature and 35r/min in the screw rotation speed. The extruded melt directly enters a die to be blown into a film.
Carrying out hot bonding treatment on the obtained blow mold and stainless steel for 0.5-1 s at the temperature
And (3) obtaining the stainless steel/blown film composite belt with high bonding strength and hot water soaking resistance at the temperature of 170-180 ℃ and under the pressure of 5-6 kPa.
Cutting the obtained composite strip into test samples with the length of 150mm and the width of 25.4mm, and testing the peel strength of the test samples by using a universal tensile testing machine; soaking the prepared composite tape sample in water at the temperature of 68 +/-1 ℃ for 168 hours, detecting the peel strength of the composite tape sample after soaking is finished, and calculating the decay rate of the peel strength of the composite tape sample before and after soaking, wherein the decay rate is (peel strength before soaking-peel strength after soaking)/peel strength before soaking.
The components of the specific examples and the test data are shown in table 1:
TABLE 1 parameters and test data for examples 1-8
As shown in FIG. 1a, the EAA/EVA and LLDPE blended film bonded stainless steel is mainly prepared by using EAA/EVAFor adhesion forces, LLDPE provides excellent mechanical properties for blended films, but this blend lacks excellent flow properties, the molecular segments are longer and the mobility of the molecular segments is limited. As shown in FIG. 1b, a tackifying resin C was added5After g-MAH and PAMS, C5The g-MAH improves the fluidity of the blend and the wettability of the film to stainless steel while providing bonding sites, and the addition of PAMS can also improve the wettability of the blended film to stainless steel and can improve the permanent bonding capability of the film to stainless steel, so that PAMS and C5The simultaneous addition of the g-MAH can increase the bonding sites of the modified blend, strengthen the movement capability of molecular chain segments and increase the effective bonding of the modified film to the stainless steel in a molten state, thereby increasing the peeling strength between the modified film and the stainless steel, but the addition of the g-MAH and the modified film is not too much, which can reduce the mechanical property of the film, cause cohesive failure of the stainless steel-plastic composite belt and reduce the peeling strength.
It should be noted that the embodiment of the present invention mainly uses a stainless steel strip as a metal composite substrate, but in the actual implementation process, other metals, such as aluminum alloy, copper, etc., have very good effects, and in fact, these metals have better composite effects than stainless steel. Due to the special surface properties of stainless steel, high-strength structural adhesive bonding between the stainless steel and various adhesives is difficult to realize, so that the compounding difficulty of the stainless steel and a plastic base material is higher than that of other metals. The compounding process provided by the invention can realize good compounding of the stainless steel and the plastic base material, has excellent hot water soaking resistance, and solves the problems in the prior art.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (5)
1. A preparation method of a polarity-enhanced and flexible tackified polyolefin stainless steel waterproof composite belt is characterized by comprising the following steps:
preparing a plastic film substrate, wherein the plastic film substrate comprises the following components:
40-60 parts of EAA/EVA,
40-60 parts of LLDPE,
C530 parts of-g-MAH,
8-12 parts of PAMS;
and (2) carrying out hot bonding on the plastic base material obtained in the step (1) and a stainless steel metal base material to obtain the stainless steel/plastic composite belt with high bonding strength and capable of being soaked in hot water.
2. The method for preparing the polarity-enhanced and flexible tackified polyolefin stainless steel water-resistant composite tape according to claim 1, wherein the plastic base material in the step (1) is subjected to twin-screw extrusion granulation and then is subjected to single-screw blow molding to form a film.
3. The method of claim 1, wherein the LLDPE has a melt index of 1.6-2.6g/10 min.
4. The method of claim 1, wherein the EAA has an AA content of 14-40%.
5. The method of claim 1, wherein the step (2) of heat-bonding the stainless steel substrate to the plastic substrate is performed at a temperature of 170 ℃ to 180 ℃ and a pressure of 5kPa to 6kPa for a time of 0.5s to 1 s.
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| CN112596183B (en) * | 2020-12-30 | 2023-06-30 | 上海网讯新材料科技股份有限公司 | Layered and easily-stripped metal composite belt |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5066542A (en) * | 1984-08-15 | 1991-11-19 | The Dow Chemical Company | Resin blends of maleic anhydride grafts of olefin polymers for extrusion coating onto metal foil substrates |
| CN104388013A (en) * | 2014-12-16 | 2015-03-04 | 广州市合诚化学有限公司 | Adhesive resin with high resistance to water soaking, and preparation method and application thereof |
| CN109054665A (en) * | 2018-06-25 | 2018-12-21 | 湖北工业大学 | A kind of metal/plastic composite band preparation method of high-adhesive-strength heat resisting water soaking |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6705680B2 (en) * | 2016-03-30 | 2020-06-03 | 株式会社神戸製鋼所 | Non-condensation type thermoplastic resin plate for adhesion of thermoplastic resin and composite member using the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5066542A (en) * | 1984-08-15 | 1991-11-19 | The Dow Chemical Company | Resin blends of maleic anhydride grafts of olefin polymers for extrusion coating onto metal foil substrates |
| CN104388013A (en) * | 2014-12-16 | 2015-03-04 | 广州市合诚化学有限公司 | Adhesive resin with high resistance to water soaking, and preparation method and application thereof |
| CN109054665A (en) * | 2018-06-25 | 2018-12-21 | 湖北工业大学 | A kind of metal/plastic composite band preparation method of high-adhesive-strength heat resisting water soaking |
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