JPS5855284B2 - Laminated film structure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION In a water storage system with irrigation canals and trenches for the movement of water, the surface of the pond, canal or trench is covered to prevent water from runoff or seepage occurring through the soil. It is necessary to prevent losses.

It may also be desirable in some cases to apply coverings to prevent water erosion of the soil.

Furthermore, it is preferred to provide protective linings for pits, ponds or lagoons containing chemicals such as acids, bases or brines, as well as protective linings for structures such as dams.

One expedient conventionally used for this purpose is a layer of cement concrete lining approximately 3 inches (7.6 CrrL) thick.

Another material used for the same purpose is the so-called asphalt board, which consists of sheets or boards about % inches (1.25 cm) thick made of wood or other cellulose fibers saturated with asphalt.

Both of these lining materials are relatively expensive;
And the application and usage are somewhat inconvenient.

Other lining materials used for the same purpose include materials made from films or sheets of olefin polymers of substantially linear structure, such as solid chlorinated olefin polymers made by suspension chlorination of polyethylene.

This material is described in Canadian Patent No. 833,665.

However, this material suffers from shortcomings in terms of dimensional stability, i.e., resistance to shrinkage when exposed to high temperatures for long periods of time, and furthermore has a low optimum strength, measured by modulus and elongation, as well as tensile and tear strength. It also lacks.

A means to overcome these drawbacks has been the use of laminated film structures with an outer layer of polyethylene with an inner layer of chlorinated polyolefin material, such as chlorinated polyethylene.

Such laminate structures also lack the necessary dimensional stability, as well as the desired modulus, elongation, tensile strength and tear and delamination resistance.

A comparison of the data set out in Table 1 below reveals the problems inherent in the known materials mentioned above and the advantages obtained by implementing the invention.

The present invention provides laminated film structures that exhibit significantly improved processability, dimensional stability, modulus, elongation, tensile strength, and tear strength and delamination resistance for use in water treatment systems. Particularly suitable.

The laminated film structure according to the invention comprises (A') a first outer layer of substantially linear polyethylene containing 25 to 50 weight percent chemically bound chlorine, the thickness of which is about 0.005 to 0.000; (B) an inner layer of substantially linear polyethylene containing 5 to 15 weight percent chemically bound chlorine, the thickness of which layer is .05 inches (about 0.013 to about 0.13 crIL); Sa is 0.
0.005 to 0.03 inch (approximately 0.013 to approximately 0
．． 076CrrL), and (C) a second outer layer having the same properties as the first outer layer, the second outer layer being adjacent to the inner layer and separate from the first outer layer; Consisting of

A composite structure using such a laminated film structure, for example, a structure in which two or more of the laminated film structures specified here are bonded together, or a composite structure using the above laminated film structure and a thermoplastic material.
Composite structures combining various layers of reinforcing materials and/or reinforcing materials are also conceivable.

For use as an outer layer of the laminated film structure of this invention,
The substantially linear chlorinated olefin polymer is a polyethylene or an interpolymer containing at least about 90 mole percent ethylene and one or more ethylenically unsaturated comonomers, preferably in suspension in an inert diluent. Manufactured by chlorination.

The polymers thus prepared preferably have an essentially linear structure and a molecular weight of less than about 1oooooo, preferably a molecular weight of about 20,000 to 300,000.

Such chlorinated olefin polymers have about 25 to 5
0. Preferably, it may contain about 35 to 45 weight percent chemically bound chlorine, and further, when the chlorine is about 25 weight percent, the relative bond JJ is about 15.
and 28 percent and a relative crystallinity of less than about 10 percent when the chlorine is greater than about 34 weight percent.

The term "relative crystallinity" as used herein refers to the ratio of the peak area of crystals to the sum of the peak areas of amorphous particles and crystals, as measured by a conventional X-ray stroke method.

A particularly preferred method for making the above chlorinated olefin polymers is described in US Pat. No. 3,454,544.

Film or sheet structures made from such materials have a thickness of about 0.01 to about 0.05 inches (about 0.01 to about 0.05 inches).
25 to about 0.127 crfL) and a tensile strength of at least about 1100 psl.

Elongation rate is 350 to 900 percent l = and 100 percent modulus is approximately 150 to 1500 psl
It is.

This type of film or sheet is described in U.S. Patent No. 339
No. 9091.

Used for manufacturing the inner layer of the laminated film structure of this invention,
The substantially linear chlorinated olefin polymer has a flowability measured as an angle of repose of 24° to 28°, a bulk density of 25 to 35 pounds per cubic foot, and a surface area of 2 to 4 square meters per gram. Characterized by
Polymers made from olefin polymer powders are preferred.

Furthermore, most of the individual particles of such olefin polymer powder preferably have a particle size in the range of 300 to 600 square meters, and a mean free volume within the particles to the volume of the individual particles in the range of 20 to 45 volume percent. It is preferable that

For purposes of this invention, the term olefin polymer as referring to the above-mentioned inner layer is intended to refer to homopolymers of ethylene, as well as less than about 20 percent aliphatic hydrocarbon alpha-mono-olefins, such as evapropylene-1, and Puden-1.

The preferred olefin polymers have absolute densities ranging from 0.90 to 0.979/c C'y, particularly from 0.950 to 0.96'1/c c, p and ASTM D
The melt intex measured by -1238-64T(E) is between 0.01 and 40 dg/min, especially 0.01 to 40 dg/min.
1 to 10 decigrams/min of polyethylene.

A preferred method for making such chlorinated derivatives of olefin polymers is described in U.S. Patent Application No. 666,844 (grant), filed March 15, 1976.

Films or sheets made from such materials have a thickness of 0.001 to 0.01 inch (approximately 0.0025
to about 0.025 crIL) and a tensile yield strength of greater than 1000 ps1 and an elongation of about 600 percent.

However, useful inner layers may be made from the conventional chlorinated polyethylene used to make the outer layers of the laminated film structures of this invention, such as mixtures of suspension chlorinated polyethylene and high density polyethylene, and may be manufactured from such mixtures. The required chlorine content in the coated layer may be provided by chlorinated polyethylene.

The chlorinated olefin polymer materials described above are supplemented with conventional additives including fillers, stabilizers, plasticizers such as epoxidized and non-epoxidized oils, flame retardants and processing aids such as low molecular weight polymers and waxes. May be mixed.

The film or sheet material used to produce the laminate structure of this invention can be produced by conventional methods.

That is, a chlorinated olefin polymer is prepared as described herein and the desired preparation is performed by substantially any method conventionally used in the preparation of vinyl chloride polymer p and vinyl chloride copolymer film and sheet material compositions. Mix with additives.

Thus, for example, the required ingredients may first be dry mixed in a mixer, for example a pump blender, and then e.g.
In this roll compounding mill, the roll temperature is approximately 240OF (115
℃) to 400°F (2r; 4°C) until the mixture is homogenized.

The mixture is then extruded into a film or sheet and then calendered to the desired thickness.

Furthermore, if the laminated structure of the present invention is preferably about 31
It may be manufactured by conventional methods using a single pass laminator at a temperature of 0OF (154° C.) and pressure applied for proper lamination of the individual layers.

The invention is further illustrated by the following examples.

All parts and percentages in the examples are by weight.

Example A) Preparation of the outer layer of a laminate structure 200 g of polyethylene were added to 4000 g of deionized water with stirring.

The polyethylene is essentially linear, unbranched polyethylene containing less than about 1 methyl group in 100 methylene units, and has a melt index of about 1 and a molecular weight of about 67,000. .

Such polyethylene is conventionally produced by a process using a catalyst containing triisobutylaluminum p and titanium tetrachloride.

Next, 8 g of calcium chloride: di
tertiary) The above product mixture was placed in a 1% gallon (5,677) autoclave along with about 0.5 cc of a 70% butyl peroxide solution in butanol and about 10 drops of a commercially available wetting agent.

The autoclave charge was then chlorinated as a first chlorination step at a temperature of about 90° C. and a chlorine pressure of about 30 psi (3.04 vs. pressure) to give a chlorine content of about 20 percent.

The charge was then chlorinated with 1 to give a total chlorine content of about 42 percent at a temperature of about 126° C. in a second cloud chlorination step.

The product was then isolated from the dispersion by filtration, washed to remove residual hydrochloric acid, and dried.

The dried ingredients were then dry mixed in a Banbury mixer to produce the following composition: Chlorinated polyethylene
100 barium-cadmium stabilizer liquid
2 Phosphate stabilizer 0.5 Epoxidized oil 3.0 Antimony oxide
3.0 Chlorinated Polyethylene Wax 2.0 Merck 10 Carbon Black 2.5 Stearic Acid 0.5 Polyethylene Wax 1 The dry mixture is then heated to about 375 to 4000F (190
, 5 to 204.4°C) and fed to calender rolls to a thickness of approximately 0.015 inch (
An essentially non-acidotropic sheet of 0.038 crIL) was produced.

Table 1 below shows various physical properties inherent in the film materials thus produced.

Ultimate elongation 〃 100φ modulus (tensile stress @ elongation rate 100φ) 〃22 wire modulus 〃Low temperature brittle ASTM D
-746 Tear resistance, 20 mil/film 0.05cIfLD-1004-59T transparent
Humidity E-96-53TE water extraction amount D-1239-55 (24 hours @73°F/22.8°C) 600-800φ --200psi (14,06kg/i) --75
0psi (52,52kg/crti') -155
°F (12,8°C) ■, 9# machine direction 2.1# transverse direction 0.262 at 10 mils (0,025 CTL)
Permeability 0.150 at 0 mil (0.05 crfL) Extraction 4 H20 Absorption B) Production of inner layer of laminate structure Slurry polymerization under low pressure i.e. less than about 30 atmospheres, temperature less than about 100°C, titanium tetrachloride Ethylene was polymerized in the presence of aluminum trialkyl and a titanium-containing component made from aluminum and diethyl aluminum monochloride to produce a high density polyethylene powder of about 30 pounds per cubic foot.

In producing a titanium-containing catalyst, carbon tetrachloride dissolved in an inert hydrocarbon solvent is reacted with diethylaluminium monochloride similarly dissolved in an inert solvent while stirring. The molar ratio of diethylaluminum monochloride and diethylaluminum monochloride is always at least 1 when all of the carbon tetrachloride is reacted.

The reaction product is then washed with an inert hydrocarbon solvent and then filtered to remove hydrocarbon solvent soluble impurities; and the molar ratio of trialkylaluminum and titanium-containing reaction products in the resulting solvent is about 0. .3:1 to about 3:
The washed reaction product was activated by adding trialkylaluminum in an amount of 1.

The polymerization mixture was stirred at a speed of about 140 rpm.

removing the polymer product in the form of a slurry from the reaction vessel;
Polymer particles were recovered by steam distillation and drying in an air slick.

When polymer particles were examined using a scanning electron microscope,
It was confirmed that all the particles were generally porous and some were molten aggregates of small particles with rough surfaces.

Screen analysis of the polymer particles revealed that the particle size distribution based on the weight of the entire powder was as follows.

1.6-14.3 72.3 larger than 540 microns
-87.6φ 320 to 540 micron 4.7-2
0.1 excellent 248 to 320 microns 0, 8-3.
3% 175 to 248 microns 0.1-0.6
% 147 to 175 micron 0, 2-1.2φ
Dense polyethylene powder of less than about 147 microns was fluidized by passing nitrogen gas in the substantial absence of oxygen in a suitable container, and then chlorine was added to the fluidizing gas to chlorinate the polyethylene powder.

The reaction was carried out at a temperature below 90°C for a time sufficient to bond 8 weight percent of chemically bound chlorine to the surface of the polymer particles.

Chlorinated polyethylene to a thickness of approximately 0.005 inches (approx.
013 cm) was calendered.

This film has a melt index of approximately 0.14 (decigrams 7 minutes, ASTM D-1238-64T(E):
b and D-1238-84T), with a percent elongation of approximately 600 (ASTMD-882-61T):
D and tensile yield strength of approximately 3920 psi (ASTM
Test method D-1412-62T).

C) Manufacture and evaluation of laminate structure The total thickness of the laminate film is approximately 0.03 inches
76 crrL), %= and approximately 48 inches wide (approximately 12
2Cr) and about 310'
The chlorinated polyethylene outer layer (A above) was laminated on both sides of the chlorinated polyethylene inner layer (B above) using a single pass laminator using a temperature of F (154°C).

This material is hereinafter referred to as structure "1".

For comparison, a laminate structure was manufactured in a manner similar to that described above, except that in the manufacture of the outer layer of A above, an inner layer made from substantially linear non-chlorinated polyethylene of the type used for chlorination was used. .

This material is referred to below as structure "2".

For further comparison, a single layer sheet having a thickness of about 0.06 inches (about 0.152 CrfL) and a width of about 48 inches (about 122 CrrL) was produced from the chlorinated polyethylene of A above.

This material is designated as structure "3". Table 2 below shows structure 1
, 2 and 3 clearly demonstrate the significantly improved properties afforded by the production of the laminated structure of the present invention.

Structure 1 (approximately 0.005 inches thick (approximately 0.013 Crf)
The overall thickness of the laminate structure of the composition (using internal layers of
The laminated structure of the invention also obtained good results similar to those described above when the amount of cIrL was set at about 122 to about 155 cIrL.
Processing was easier compared to the composition structure of Structure 2.

More specifically, the laminated structure of the present invention had a production yield of 10φ or more compared to the production of Structure 2, and there were no irregular edges commonly seen when producing Structure 2 materials. .

These properties have enabled the production of laminate structures that are significantly wider than those available with Structure 2 type materials, ie, up to less than about 60 inches (about 152 cfIL).

The laminate structure of this invention provides tear resistance, delamination resistance and cracking as a result of freeze-thaw cycles and as a protective lining in newly constructed water-containing ponds, including ponds where the soil is not fully consolidated. It exhibits excellent resistance to winding and ripple effects when used.

The laminated structure of the invention also provides excellent oil and chemical resistance when used as a protective lining in ponds, lagoons or ditches used for oil and chemical storage or transfer. show.

The laminated structures of this invention can be easily welded together by the use of conventional solvents such as methyl ethyl ketone, toluene and xylene.

Such laminated structures can be used for lining canals, ditches, ponds and water treatment systems, and can supply sheet material of the desired width in the form of rolled rolls to the working position.

The sheet can then be easily removed from the roll and cut to the desired or required length.

If desired, the individual film housings or sheets can also be welded by conventional solvent welding and/or dielectric welding methods.

Claims (1)

Claims: 1. A laminated film structure comprising: (A) about 25 to about 50 weight percent chemically bound chlorine;
A first outer layer of substantially linear olefin polymer, this layer having a thickness of 0.005 to 0.05 inches (approximately 0.013
to about 0.13 cIrL). (B) an inner layer of substantially linear olefin polymer containing 5 to 15 weight percent chemically bound chlorine, the layer having a thickness of 0.005 to 0.03 inches (0.013 to 0.03 inches); .076c*), and (C) a second outer layer having the same properties as the first outer layer, this layer being adjacent to the inner layer and separate from the first outer layer. structure. 2. The first outer layer and the second outer layer have a relative crystallinity of 15 to 28 percent when containing 25 percent by weight of chlorine, and a relative crystallinity of less than about 10 percent when containing about 34 percent by weight or more of carbon and chlorine. and wherein the layer has a tensile strength of at least 1100 pounds per square inch, an elongation of 350 to 900 percent, and a 100 percent modulus of 150 to 1500 psi. The laminated film structure according to item 1. 3. A substantially linear olefin polymer whose inner layer exhibits flowability measured at an angle of repose of 24° to 28° and is characterized by a bulk density in the range of 22 to 35 pounds per cubic foot and a surface area of 2 to 4 square meters per gram. wherein the polymer is composed of individual particles, the individual particles having a particle size primarily from 300 to about 6
3. The laminated film structure of claim 2, wherein the laminate film structure is in the range of 0.00 microns and the mean free volume within the individual particles is 20 to 40 volume percent based on the total particle volume. 4. The method of claim 3, wherein the first outer layer and the second outer layer are layers made of substantially linear polyethylene containing about 42 weight percent chemically combined chlorine. Laminated film construction. 5. The laminate film structure of claim 4, wherein the inner layer is a layer made of substantially linear polyethylene containing about 8 weight percent chemically bound chlorine. 6 The inner layer thickness is approximately 0.005 inch (approximately 0.013
cIrL), and the overall thickness of the laminated film structure is 0
．． 6. The laminated film structure of claim 5, wherein the laminated film structure has a width of less than about 60 inches (about 150 cm). 7. A laminated film structure according to claim 1, wherein the inner layer is a layer made from a mixture of high density polyethylene p and chlorinated polyethylene.