DE2724866A1 - PAPER- OR PAPER-LIKE LAMINATE WITH INTERLAYERED PLASTIC SULFUR AS ADHESIVE - Google Patents

Description

272486S

3 1st Ma: 197? BP'f. rr ^ i ^ PF & BE! L

FRANKFURT AM MAIN 80

Our No. 21 189 Pr / br

Chevron Research Company San Francisco, CaI., V.St.A.

Paper or paper-like laminate with layers in between! plasticized sulfur as an adhesive

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The invention relates to plasticized sulfur, which by special Heating and cooling was made and which is a good glue that works as a binder or adhesive for Paper laminate, especially for pipes made from it, is used.

Plasticized sulfur has been described in various references, for example by JIJin in Chemistry of Plasticized Sulfur, Petroleum Division, ACS Symposium, Vol. 19, No. 2, March 1974, pages 234 to 241, and by C. Kinney Hancock in Plasticized Sulfur Compositions for Traffic Marking, Industrial and Engineering Chemistry, Vol. 46, No. 11, November 1954, pages 2431-2435. Exemplary patents describing plasticized sulfur and heating temperatures at which plasticized sulfur forms include U.S. Patents 2,169,814 "bonding and coating Product" (heating temperatures of 150 to 16O ⁰ C); US Pat. No. 3,306,000 "Construction Method" (heating ^{temperatures from 135 to 175 °} C.); U.S. Patent No. 3,316,115 "Marking Composition" (heating temperature of 16O ⁰ C); U.S. Patent No. 3,371,072 "Sulfur Resins" (heating temperatures of 100 to 200 ⁰ C, preferably 110 to 16O ° C); US Pat. No. 3,384,609 "Plasticized Sulfur" (heating temperatures of 120 to 250 ° C., preferably 140 to 160 ° C.); U.S. Patent No. 3,434,852 "Plasticized Sulfur Compositions" (heating temperatures of 50 to 25O ° C, preferably 100 to 200 ⁰ C, and Examples 13O to 170 ° C); U.S. Patent 3,447,941 "Sprayable Sulfur Road Marking Compositions" (heating temperature of 150 ° C); U.S. Patent No. 3,453,125 "Plasticized Sulfur Compositions" (heating temperatures of 120 to 25O ° C, and in Examples I38 to 170 ⁰ C); U.S. Patent No. 3,459,717 "Sulfur-Based Plastic Compositinn" (heating temperatures 115-200 ⁰ C, preferably l40 to 170 ° C); U.S. Patent No. 3,465,064 "Adhesive Plasticizes Sulfur Containing to olefins polymer" (heating temperatures of 100 to 200 C, preferably 140 to 15O ⁰ C);

U.S. Patent No. 3,560,451, "Plastic and Nonflammable Sulfur Composition" (heating temperatures of 120 to 18O ° C, preferably I ¹ IO to 16O ° C); U.S. Patent 3,6HO,965 "Thermoplastic Sulfur Containing Polymers"; U.S. Patent No. 3,674,525 "Plasticized Sulfur Compositions" (heating temperatures of 50 to 250 ⁰ C and in the examples, about 155 ° C); US Pat. No. 3,676,166 “Plasticized Sulfur Compositions” (heating temperatures from 2k to 20H ⁰ C, preferably 121 to 177 ° C, and as an example 149 ⁰ C); U.S. Patent No. 3,734,753 "Plasticized Sulfur Compositions (heating temperatures of II8 to 25O ° C, preferably 15O ⁰ C); US Patent No. 3,787,276" Corrugated Cardboard Containing Sulfur Foam "(heating temperature of 110 ⁰ C) and US-PS 3 823 019 "Mine Wall Coating" (heating temperatures from II6 to 160 ° C., preferably 130 to 160 ° C.).

As can be seen from the examples of the foregoing patents, the temperatures suggested by the patents for heating or for carrying out a reaction to obtain the plasticized sulfur masses are generally about 150 ^° C ¹ '753, column 2, line 50 with respect to the production of plasticized sulfur compositions: "Preferably, the temperature of the reaction mixture is maintained at about 150 ⁰ C, since pure sulfur at 16O ° C becomes viscous and higher temperatures increase the process costs."

"Elemental Sulfur", edited by B. Meyer, Interscience Publ. (1965) describes in Chapter 5 the sharp increase in Sulfur viscosity at about 159 ° C. Chapter 8 of "Elemental Sulfur" describes the following:

"Both the arsenic-modified and the phosphorus-modified systems have a dark red color and are unpleasant Odor and tend to crystallize out when exposed to light and air. Arsenic-sulfur systems are more stable, and such materials have become a variety of

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Processed products, including lenses, prisms, tubes and fibers. "

"Polymer sulfides and polysulfides are more promising Modifiers for elemental sulfur and tend to stabilize the material in a plasticized form. These Materials form viscous liquids when heated with sulfur to temperatures above their polymerization point (159 ° C), which show pronounced polymeric properties on cooling. Elemental sulfur crystallizes from these masses only after comparatively long periods of time, depending on

Concentration of the polysulfide polymers used. Masses,

which contain only 10 to 15 % of the polymer (ethylene tetrasulfide), remain in a polymeric form after heating to 160 to 175 ° C for several days before they completely crystallize out. Larger amounts of ethylene tetrapolysulphide result in flexible materials, the properties of which remain fairly unchanged for several weeks, after which, however, hardening takes place when the sulfur crystallizes out ".

"Mixtures of ethylene polysulfide and sulfur have been studied extensively by Tobolsky et al. (J. of Polymer Sci. A2, 1987 (1964)). Both linear and crosslinked systems have been made. Each produces extensive supercooling of the sulfur. Systems that are Ί0 % Containing supercooled liquid sulfur, remained free from crystallization for over 3 years. "

The invention also provides a method of making laminated plumbing pipes or tubes. To the examples patents in this area include U.S. Patents 1,9 ^ 3,501

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"Manufacture of Paper Tubes", for example the manufacture of shotgun shell cases; U.S. Patent 3,055,2? 8 "Reinforced Plastic Pipe"; U.S. Patent 3,323,962 "Reinforced Resinous Tubular Laminates" for Used in electrical insulation etc. and US Pat. No. 3,767,500 "Method of Laminating Long Strips of Various Materials".

According to the invention a composition is provided that contains plasticized sulfur, wherein the composition is prepared by the plasticized sulfur is heated to a temperature between I60 and 220 ⁰ C and then the hot plasticized sulfur is cooled in liquid form to a temperature below 16O ° C , whereby a liquid sticky plasticized sulfur is obtained. Preferably, the hot plasticized sulfur to a temperature below 155 ° C, for example a temperature of 150 ⁰ C or is cooled below. The sticky plasticized sulfur tends to remain sticky or glue-like longer than plasticized sulfur that has not been subjected to the heat treatment according to the invention. In addition, it has been found that the plasticized sulfur can generally be cooled to a temperature below its normal melting point to give a supercooled plasticized sulfur which has good adhesive properties. In addition, the plasticized sulfur, especially when it has been plasticized with dicyclopentadiene, shows lower viscosity at high temperatures of about 160 to 220 ° C., preferably 170 to 210 ° C., than pure sulfur at these high temperatures. This makes the plasticized sulfur relatively easy to work with to achieve the sticky, cooled, plasticized sulfur mass. The relatively reduced viscosity compared to pure sulfur is not as reduced at the high temperature when fillers such as talc are incorporated into the mass.

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The plasticized sulfur contains sulfur, which with an organic solvent that is able to plasticize the sulfur, is implemented, as described in more detail below. Preferably the plasticized sulfur is added prior to the cooling step to a temperature between 170 and 210 C, particularly preferably 175 to 210 ° C, brought. The stickiness is increased by incorporation increased by materials such as talc, mica and other finely divided mineral fillers. In the case of the mass, which is only an organic one If contains plasticizers, stickiness will not normally develop unless the mass is impregnated or is on a substrate layered like paper or paper-like material.

According to a preferred embodiment of the invention, an adhesive is provided in which the adhesive was produced according to the steps described above. It has proven to be particularly advantageous to use the compositions according to the invention as adhesives or binders after they have been cooled somewhat and preferably while they are in the supercooled liquid state and not after the compositions have reached constant equilibrium and have become solidified. The use of the masses after cooling, and preferably while they are supercooled liquids, relatively facilitates easy handling at or about room temperatures from HO to 50 ^° C., usually about 12 to 38 ^° C.

The adhesive mass has the advantageous properties usually waterproof and chemical resistant, especially acid resistant.

The one achieved on the way via the heat treatment according to the invention Mass is particularly advantageous in that it retains its liquid properties longer when cooled, so that in the case of the thermal contraction, relatively low stresses are generated by the cooling, compared to what would be the case

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would with normal solidification at normal melting point and cooling of the solid. With such normal cooling the tensions produce cracks or throw up the material. Therefore, there is an advantageous application of the composition according to the invention in areas where minimal jumping and similar is important. Therefore, the mass is advantageously used for the production of castings and / or molds that you want to avoid or reduce jumping or the build-up of tension during cooling.

The composition of the invention is also advantageously used for Manufacture of paper products for packaging, for making containers such as barrels or cartons, and for making Building panels and components applied. The mass is suitable as a reinforcement medium for paper and wood products as well as an adhesive and can therefore advantageously be used for laminating Layers of paper or paper-like material are used to make containers in which the adhesive mass is used to hold them together the paper or paper-like material is used. The mass can be used as an adhesive, simply around the To hold layers together, however, it can also be used on the edges or seams of a container to seal the To hold seams or different sides of the container together.

According to a further preferred embodiment of the invention a laminated conduit or pipe is provided. The installation pipe or pipe is made by Layers of paper or paper-like material are laminated to the plumbing pipe or form using the plasticized sulfur, preferably the plasticized sulfur glue described above, to form the layers to stick together.

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Suitable types of paper or paper-like material that are used to make plumbing pipes or ducts or also can be used to produce other objects such as containers using the compositions according to the invention are kraft paper, Newsprint, tissue paper, felt, cardboard, bagasse, cotton, natural or synthetic material, polypropylene felts and piping in woven, random, or spun form.

The sticky compositions according to the invention can advantageously Use for the production of components due to the adhesive character of the mass. Components can be used the mass can be connected to each other, and also components such as beams or posts can be built using the Mass as a stiffening and binding agent. Advantageously, beams or posts and the like can be made of synthetic or natural fibers or wood products, where the plasticized sulfur mass is used to make the components or To hold parts together and to stiffen the components.

The present invention is based inter alia on the fact that plasticized sulfur, which has been prepared as described above, possesses particularly favorable tack after cooling and also tends to have tack even below normal Maintain solidification temperature and thus advantageous properties Has as an adhesive or binder. Heating to a lower temperature, for example 150 ° C, like it typically applied to heretofore plasticized sulfur results in unusable plasticized sulfur masses as in the present invention, especially the sticky liquid masses that are immediately after cooling according to the invention can be obtained.

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Although the composition of the invention can be used both after heating to a temperature above 160 ° C. and cooling to a temperature below 160 ° C., the hot plasticized sulfur can also be used while it is at a high melting temperature, which is above 160 ° -Temperature may or may not be the case. The hot molten plasticized sulfur have been heated according to the invention in each case to a temperature above 16O ° C and preferably above 170 ⁰ C, so that the composition of the invention mass then either injsitu or as a transition after the application of ^it ^ hot plasticized sulfur on paper or another substrate can be obtained. For example, paper or another substrate can be impregnated with hot plasticized sulfur above the melting point and then cooled, for example below the melting point, in order to obtain a still sticky surface, as is the case with self-adhesive tape. The surfaces obtained in this way are then preferably connected to one another or to another object before the cooled, plasticized sulfur solidifies. Of course, the material will only remain tacky or not set for a limited time, this time limit being a function of the time and extent of heating and the amount and type of plasticizer used.

The term "liquid" plasticized sulfur as used herein Used includes non-solidified and non-rigid plasticized sulfur. For example plasticized sulfur that is still sticky or that has not yet solidified sufficiently to with the plasticized sulfur to stiffen impregnated paper, called "liquid" plasticized sulfur.

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Contain plasticized sulfur compounds provided according to the invention

preferably mainly sulfur. The plasticized sulfur preferably contains more than 50% by weight and is particularly preferred about 70 to 90 weight percent sulfur or more.

As used herein, "plasticized sulfur" usually has a somewhat lower melting point than elemental sulfur. In addition, plasticized sulfur requires a longer crystallization time, ie the rate of crystallization of plasticized sulfur is slower than that of elemental sulfur. A useful way to measure the rate of crystallization is as follows: The test material (0.040 g) is melted on a microscope slide at 130 ° C and then covered with a square cover slip. The slide is placed on a hot plate and maintained at a temperature of 78 ± 2 ° C, which is measured on the slide using a surface pyrometer. One corner of the melt is seeded with a crystal of the test material. The time required for complete crystallization is measured. Plasticized sulfur is thus sulfur that contains an additive that increases the crystallization time within the experimental error limit, ie the average crystallization time of plasticized sulfur is greater than the average crystallization time of elemental sulfur. For the present application, plasticizers are understood as meaning those substances which, when added to molten elemental sulfur, cause an increase in the crystallization time compared to that of elemental sulfur itself. In a test arrangement requires elemental sulfur is 0, ¹ I ¹ I minutes to crystallize under the above conditions, while sulfur 3.8 JC contains a phenol-sulfur adduct, as is described in DT-OS 23 2 ¹ I 175, , Took 2.9 minutes. Sulfur with 6.6 and 9.9% of the same phenol-sulfur adduct required 5.7 and 22 minutes, respectively.

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The inorganic plasticizing agents include iron, arsenic and phosphorus sulfides, but the particularly preferred plasticizing agents are organic compounds that can react with sulfur to obtain sulfur-containing materials, such as styrene, α-methylstyrene, dicyclopentadiene, vinylcyclohexene, the adducts of aromatic compounds and Sulfur of DT-OS 23 2 ¹ »175 as well as the aromatic compounds which are used to prepare these adducts, aromatic or aliphatic liquid polysulfides and the viscosity control agents as described in US-PSS 3 67M 525, 3 ^ 53 125 and 3 676 166 to be discribed. The preferred aromatic plasticizing compounds are styrene and the phenol-sulfur adduct of DT-OS 23 2 M 175. The preferred aliphatic compound is dicyclopentadiene.

A preferred plasticized sulfur substance contains dicyclopentadiene, Sulfur, fiberglass and talc. It has also been found that asbestos is advantageously used in place of fiberglass in the above plasticized sulfur substance can be used.

The elemental sulfur can be either crystalline or amorphous and can contain small amounts of impurities such as they are usually found in commercial sulfur. Optimal proportions of sulfur and the other components the mass can vary considerably. However, proportions of sulfur from about 73 to 97 weight percent are generally satisfactory.

Dicyclopentadiene is readily available commercially, generally in a purity of about 96 % or greater. It is preferably used in the preferred plasticized sulfur compositions described above in an amount of about 1 to 7 parts by weight.

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The glass fibers of the preferred plasticized sulfur mass are preferably used in the form of comminuted fibers, the fibers generally having a length of about 0.79 mm to 6.35 mm, preferably an average length of about 1.58 mm. These fibers, generally made of high silica glass, are readily available commercially, often coated with a starch binder. However, the type of glass is not critical as long as it provides the resulting mass with sufficient shear force, preferably a shear force of about 28.1 to 56.2 kg / cm. The glass fibers preferably comprise about 1 to 5 wt -.% Of the mass of the invention.

That in the preferred dicyclopentadiene-sulfur-fiberglass-talc mass The talc used is preferably a slate type or a compact variety such as steatite. Impure varieties such as soap stone can also be used. This ingredient is preferably used in an amount from about 1 to 15% by weight of the mass is used and serves a double function namely, it gives the mixture thixotropy and disperses the glass fibers within the mass, causing agglomeration of the fibers is prevented.

example 1

A plasticized sulfur was made by adding about 2 weight percent organic plasticizer, namely dicyclopentadienes mixed with molten sulfur.

Coupons made from 0.203 mm thick Kraft paper were melted with the plasticized sulfur treated at different temperatures. The paper coupons were plasticized in the melted one Immersed in sulfur and then hung up to

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air drying temperature. The time after the first dry spot appeared, after the coupons were 50 % dry, and after they were 95 % dry, was recorded. The term "dry" as used herein means setting and tacking non-stick rather than drying by evaporation of a solvent as is normally the case.

The impregnated coupons contained about 85 wt. plasticized Sulfur. In practicing the invention, the paper or paper-like material can be impregnated or coated with about 5 to 90 wt. Ϊ of plasticized sulfur (based on the Paper and plasticized sulfur), but preferably about 10 to 50 wt .- * are used. So the 85 Gew.-JJ are something higher than normal.

After the plasticized sulfur ^{had been heated to 150 °} C. for 1 or 2 hours, it solidified and very quickly became non-sticky after being impregnated on the paper. See Table I. below.

Table I.

Paper impregnation at constant temperature Beginning Drying time, minutes % dry Plasticized
sulfur fast
2
3
3 50% dry 95 0.1
15th
17th
17th Heating time fast
6th
8th
10 at 1500c, h 1
3
1"
8th

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When heating the plasticized sulfur to higher temperatures Drying or solidification took longer than 150 C. See Table II.

ver
deleted Drying time, minutes 5 dry Table II Heating
time, hours Beginning 50? dry 95Ϊ 13th 9 1 3 8th 22nd Paper impregnation for different
Temperatures 1-1 / 2 5 16 22nd Plasticized
sulfur 1-5 / 8 3 23 30th Heating levels 1-3 / 4 4th 47 1 hour at 160 ° C 2-1 / 4 9 Increase in
Temperature up
17O ⁰ C Remove
from the oven
and cooling
to 135 C. Increase in
Temperature up
15CTC Increase in
Temperature up
195 ^D C

When comparing the data of Table I and Table II wherein is also noted that when plasticized sulfur to I60 to 17O ⁰ C or is heated up, a plasticized sulfur with delayed solidification is faster (compared to the use of lower heating temperatures), the Solidification is delayed even more and the retention of the adhesive properties or tack is extended even more.

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Example 2

A plasticized sulfur mass containing sulfur, dicyclopentadiene, Containing talc and fiberglass was prepared as follows:

A stainless steel beaker equipped with a stirrer was charged with 90 parts of sulfur, which was then heated to melt. While the temperature of the stirred, molten sulfur was kept at 138 ^° C., 1.6 parts of dicyclopentadiene were added. After a reaction time of 10 minutes, 6.4 parts of talc were added. After the talc had been mixed well, 1.8 parts of cut 6.35 glass fibers (Owens-Corning No. 63O glass fibers) were then added. Stirring at 138 ^° C. was then continued for a further half an hour. After cooling to room temperature, this material forms a hard, opaque mass that can be broken into smaller pieces for easier handling.

The plasticized sulfur mass obtained as described above was used for the construction of a container, in particular for the construction of a box, which had a substantial degree of water resistance. Thus, 2 g plasticized sulfur were about done on a hot plate and heated to a temperature of about 185 ⁰ C. The molten material was spread with a spatula to a thickness of about 0.39 mm. Then a piece of Kraft paper about 10 × 10 cm in size was placed on the molten, highly viscous plasticized sulfur and gently pressed down over its surface with the spatula. While it was still on the hot plate, an additional 2 grams of plasticized sulfur was placed on this kraft paper and allowed to melt. This material was the same over the entire top

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Surface of the paper distributed. Then a second piece of kraft paper about 10 10 cm in size was put over the first and pressed on with a spatula. Finally , a third 2 g serving of plasticized sulfur was placed on the two layers of paper and allowed to melt and spread.

While it was still hot (about 185 ⁰ C) impregnated with plasticized sulfur-ply laminate of the hot plate was removed and cooled within about 10 seconds at room temperature. The laminate was plastic and tacky on both surfaces. It was made into a box by folding the sides up and overlapping the corners. The seams were closed by pressing the edges together. This box held water for more than 24 hours without leaking.

Example 3

The plasticized sulfur of Example 2 was used to produce a laminate of 12 layers of newsprint with a size of approximately 7.6 × 7.6 cm by the method described in Example 2. After the zwölflagige laminate was removed from the hot plate and was rapidly cooled to 20 ⁰ C, it was rolled into a tube that was closed mm by pressing the edge with an overlap of about 2.7. After about half an hour, the pipe lost its plasticity and hardened into a rigid tubular structure. The pipe was not affected by immersion in water.

For: Chevron Research Company

San Francisco, / Pal., V.St.A.

Dr. PtTj. woiff

Lawyer

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Claims (6)

Patent claims: 1. ^λ paper or paper-like product made of layers which are laminated together by a plasticized sulfur adhesive, characterized in that the plasticized sulfur adhesive is heated to a temperature between 160 and 220 ⁰ C to obtain a molten adhesive with low viscosity manufactures. 2. Product according to claim 1, characterized in that the hot plasticized sulfur obtained in the heating stage is cooled in liquid form to a temperature below 150 ^° C., to obtain a liquid adhesive. 3. Product according to claim 1 or 2, characterized in that plasticized sulfur as a plasticizer dicyclopentadiene, aliphatic polysulfides, aromatic Contains polysulfides or mixtures thereof. 4. Product according to claim 1 or 2, characterized in that the plasticized sulfur contains sulfur, dicyclopentadiene, asbestos or fiberglass and talc. 5. Product according to claim 1 or 2, characterized in that the plasticized sulfur is brought to a temperature heated between 175 and 210 ° C. 6. Product according to claim 2, characterized in that the hot plasticized sulfur to a temperature below its normal melting point cools. B09850 / 0U8 ORIGINAL INSPECTED