SI8411053A8 - Process for making starch product resistant to flame - Google Patents

Description

PROCEDURE FOR THE MANUFACTURE OF A STARCH FLAMMABLE PRODUCT

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The invention is in the field of starch processing, and is particularly relevant to. a process for the production of flame-resistant starchy products which can be used as adhesives and binders in the production and processing of paper and paperboard, flame-resistant building materials, insulating materials and complex materials, paints, coating colors, sorting agents, protection agents and thermoplastic materials.

According to the International Patent Classification, the invention is classified in classes C08B 31/00; C08L 3/04, C09J 3/06 and D21H 1/24.

The invention solves the problem of the flammability of starch products used for various purposes where flame resistance is required.

The state of the art __ _ _

Starches, possibly physically or chemically modified, are known to be suitable for many technical purposes and to be used, alone or in combination with synthetic polymers, as relatively inexpensive fillers, thickeners and / or binders and adhesives for wet and surface sorting in production and processing of paper and in the folding, as well as for coating and binding of paper and cardboard, in the production of complex materials, and as binders in paints, adhesives, fillers, powders and coating preparations, many of the requirements imposed by these applications being met by the choice of the correct starch product and / or additives.

However, known starch products often have difficulty * due to unsatisfactory viscosity stability, water resistance and / or synthetic compatibility. noimers, and especially due to lack of thermoplastic properties and, therefore, high flammability and lack of ability to seal in heat. Many attempts have been made to address these shortcomings, but they have only been moderately successful because, especially with respect to the two last surviving individuals, the improvements achieved were limited and required a considerable amount of effort.

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This is particularly applicable to improving the resistance of starch to flame, which, according to the prior art, was achieved by mixing and, by extension, the reaction of starch with phosphate, by means of which processes can be obtained which are, in themselves, sufficiently resistant to flame, by themselves largely not suitable for imparting adequate flame resistance to materials. treated with them, such as paper, cardboard or rendered textiles, coated or coated therewith and / or plastic material! mixed with them, while in respect of other properties requiring improvement, in particular the ability to seal in heat, do not give satisfactory results.

9Bis_tehnicko2_resenja_sa_grimerima_izodenja

That's why he's a sailor. the object of the present invention is to overcome these disadvantages of the earlier sciences and to specifically provide new low-cost starch products characterized by high flame resistance and characterized by other mournful properties, particularly high high-strength stability, high curing strength on all types of upstairs such as paper, plastic cardboard, glass and mineral fibers, metal and plastic materials !, foam and / or mineral sheets and stone, and.'or further characterized by nu zermopls - flexible and water-repellent, clear-breathable films which are heat sealed and flame resistant.

According to the invention, the invention is a process for the production of flame-resistant starch tritium water characterized by reaction to 40 ° C to 25 ° C, gelatinized starch or physically or heai modified gelatinized starch with 3 to 40% by weight of dry matter starch substances of one or more sulfomates selected from the group consisting of alkaline, alkaline earth and ammonium sulfates in the presence of at least 30 wt. % water based on total weighted reaction Ecisse.

Since sultanates are commonly known flame retardants used, for example, for making flame resistant textiles and papers (USP 2,142,110, 2,212,152, and 2,452,954 X BE-PS 904,524), some improvement in starch resistance to pla is reasonably expected to incorporate sulfamate incorporation into O3, although not to the extent actually achieved by the present invention and, in particular, the starch products of the process of the invention could not be expected to be obtained by the reaction of gelatinized starch with sulphate (s), in addition to the unexpected high flame resistance, also exhibit extremely good viscosity, stability, good compatibility with synthetic polishers, great bonding properties and water resistance and will for the most part even be thermoplastic and heat sealable.

Starch, whether chemically or physically gelatinized or modified, may be already Latinized ir. you are here.

The sulphamates suitable for the purposes of the invention are generally all alkaline sulphamates and alkaline earth sulphamates, but they are preferably ammonium sulphamate and earth alkaline sulphamates, especially calcium sulphamate, because sulphamate starches are made aa by alkali metal sulphamates and, above all, by calcones, when used as or in paper glue (s), they give opiates that do not tend to turn yellow.

The starch composition of the invention is determined by the amount of sulfamate used in the reaction which, according to the invention, is desired; however, in the interval from 5 to 33, preferably from 7.5 to 20, and most preferably from 1 to 25, based on dry starch co-existence.

that by adding as little as 5 wt.% aracic sulfamate, it is possible to dc-be starchy products of a process that ευ not only have high flame retardant or flame retardant properties, but as a rule exhibit clearly improved film-permeability and film elasticity properties .

It has been gained from the experience that from the sulfamate content of about 10 to 25 wt. percent by weight of starch, the products of the process of the invention show good heat-sealing properties. Ns example. paper that I coated with a film of acrobat product in an amount equivalent to 10 heating aid (approx.

150 ° C) and slight pressing can cause the ss to adhere so firmly to the other paper that after cooling the bonds, the asak cepabjaa Ylakana can be separated.

It has been found that the starch products of the process of the present invention with medium to high sulfonate content are not alone

inherently flame retardant, they can also be used to finish with flame resistance. For example, a flame-resistant plate is obtained by coating both sides of the plate with a weight of 2 2

250 g / m with 10 g / m starch product of the process of the present invention with a sulfate content of 20 wt. 1.

Starch products according to the invention with a high sulfamate content (varying from about 30 to 33% by weight, based on experience) are thermoplastic preparations characterized by a softening temperature of about 12G ° C, which after hardening will solidify into solids, solids and tubs. are exposed to intense hugging (gas flames) will decompose (odor or caramelization).

The starch products of the process of the invention are chemical compounds of a hitherto undefined structure that can be inferred, inter alia, from the fact that, by their chemical and physical properties, they are clearly distinguishable from cdgvcd physical mixtures of pre-gelatinized starches and dry starch mixtures or non-heated starches. and sulpharate solutions and on the basis of the fact that the sulphate component cannot be separated by extraction.

The products of the invention may include not only pure sulphate starch but also products which, in addition to sulphate starch, contain at least one synthetic polymer in an amount preferably up to about 3G% by weight, based on the total weight of the finished starch product, specifically some vinyl polymer, wherein the products in which the (co) synthetic polymer (1) is incorporated are the polymerization of at least one vinyl noromer and / or vinyl prepolymers in situ, specifically in the presence of a sulphate starch which serves as a protective colloid.

An orc.alaska procedure based on the following r.alazim.a:

i3UjLxsmatlt for disconnecting cd of other modirl-acai syrups, practically does not react with non-gelatinized starch. With dry cold-swollen (pra-gelatinized) 3-starch the reaction is practically non-existent, and even mixtures of aqueous solutions of desclatinized starch and sulfamate do not react in the cold state.

- 5 However, with an aqueous mixture of gelatinized starch and salfamate, drying with warming is often sufficient to cause a reaction that leads to a clear effect on the properties of the reaction product and is intended to be diligent in the process of the invention. However, it was found to be the most! the results obtain gelatinizing starch by official methods, for example, in non-continuous or continuous cooking vessels, in extruders or on heated rollers, and the reaction (in situ) of gelatinized starch with eulfamate (s) at one stage of the process. This is another indication that chemical reactions, probably esterification, are carried out between the starch and the aulfamate of the code starch products of the invention are formed, and these reactions are promoted in this embodiment of the process of the invention by holding the reaction at elevated temperatures, · achieves exposure to reactive centers of skrcha gelatlniz ciiom in tu.

As already mentioned, the starch reaction with sulfamate (s) must be boiled in the presence of water, empirically, in an amount of at least about 30% by weight. fc na. based on the total mass of the reaction mixture.

The optimal reaction temperature will naturally depend on the environment in the specific case, so according to the situation, any person skilled in the art can easily choose it for their purposes within the aforementioned interval, taking into account the principles that higher temperatures will accelerate the reaction, but will also increase the risk of secondary or lateral, reaction (breakdown) and yes, the kaua uses non-gelatinized starches, the temperature of the gelatinization must at least temporarily be superimposed.

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The reaction mixture obtained in the reaction can often be used as such or can be further processed by drying and / or incorporating synthetic polymers.

The amount of synthetic polymers to be incorporated into the sulfamate: starch can in principle be chewed at will; therefore, the aforementioned amount of 80 wt. % based on the mass of the total dry substance is not an absolute maximum, but rather a Smyrian vorticity at which the eulfsmatin starches were determined to be still clear in the starch products of the invention.

- 6 Although, in the manufacture of starch * products of the present invention containing synthetic polymers, they may generally be able to be incorporated into the sulphate starch according to certain physical and / or chemical processes, for example, also by mixing in the dry state, experience has shown that to obtain starch products of optimum properties, it is best to react the sulfamate starch with the polymer (s) in a particular, preferably aqueous, dispersion, specifically by polymerizing suitable monomers and / or prepolymers. in situ in aqueous colloidal dispersion of starch / sulfamate reaction product.

and particularly simple, useful and therefore desirable process for the production of starch products according to the present invention ensures that starch reacts with sulfarnate (s) on heated rollers commonly used to make cold-swollen starches, optionally with in situ gelatinization, and then optionally the reaction mixture sushi.

for this embodiment, it is preferable to use an aqueous dispersion having a total starch and sulfamate dry matter content of 30-70, more preferably 36-60, and most preferably 40-55% by weight.

iaaa polar material which is yet more common 2a for the purposes of the present invention may be any type of non-unidentified or physically or lianically modified starch, modified, specific degrading, acylovaii, tariff and / or oxidized crystals are desirable.

as mentioned above, the products of the process of the invention are preferably used as or in adhesives and binders with paper, cardboard, breast material, insulating materials, plastics, textiles, glass and mineral fibers, and are characterized by the fact that mostly in addition to being flame resistant, although very water soluble they still give bonds or coatings repellent to the water and, after drying, generally produce clear, breathable, pliable, elastic and / or heat sealant films. Further, many of the process products are suitable for product r. solid flame-retardant foams and / or as thermoplastic t * The following examples illustrate the invention and unless otherwise explicitly n

And voted. percentages are always up.

Example 1

20% Suspension of acidic and degraded starch (having a viscosity of 50 mPa with 5% aqueous solution, mercr.about 5C ° C with a Brookfield viscometer, spindle 1,20 RPK) in water is mixed with 25% ammonium sulfamate , based on the dry starch substance, after which the mixture was heated at S5 [deg.] C. for 25 minutes at a full value of 4.5. The resulting sulfamate-starch solution after drying formed a non-flammable, water-repellent, flexible, breathable film.

Example 2

400 parts by weight of oxidized starch (viscosity of 10% aqueous solution 50 rJ? A.s at 60 ° C (Brookfield viscometer, spindle 1,

PPM) together with the 0 parts by weight of ammonium sulfamate are suspended in 480 parts by weight. parts of water. The suspension is gelatinized using a drying roller and dried at a vapor pressure of 9 bar.

The resulting flaky product was easily dissolved in water at room temperature.

When dried, the solution became flame-resistant, highly flexible, suction. for water, clearly ventilated and sealed in heat

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An adhesive made from 20 wools of the described product for dissolution in 390 parts by weight of water showed remarkable stability over vi3xozitut and provided a very good, flame-resistant bonding of various materials, such as paper / cardboard, - norton, paper / aluminum foil cardboard, mineral fibers and / or 3ta /. linen fibers, rigid foams of polystyrene, phenolic resins or polyurethanes, wood, plastics, minerals and stone.

This solution can also be used for bonding textiles and fiberglass threads, for finishing fabrics made from them, as an additive in protective coatings, '- for finishing packaging materials made from paper, cardboard or wood. Material so torn or retained

The flat 1X1 * flames itself, flushes out the water X »is apt at heating.

- 8 Example 3

100% by weight of the base. 30% of the sulfamate starch solution, made as in Example 1, is mixed in 1ύΰ masses. - commercial grade polyvinyl acetate dispersion parts. The adhesive thus produced was suitable for multiple bonding (see Example 2), tightened very quickly, and provided flame-resistant, water repellent and sealing bonds.

Example 4

The scrcb-sulfamate solution was made as in Example 4 with a dry substance content of 15.4% and a conventional starter. added to it, after which 37.7% by weight of vinyl acetate n

monomer and polymerized for 2.5 hours at 70'C.

The PVA dispersions thus obtained showed the following characteristics:

Guva Substance ·

Viscosity (Brookfield so. 3) 52.5%

RPM: 2,300 mPa.s

20 PPM; 1,670 th most common mPa.s 50 RPi-5; 1, oh mPa.s 100 odj <; 800 mPa.s sobine film

irrigated, water repellent, olair.en ablated, '* · · ·. tonloti.

Example__5

Paper impregnated with a sulfaiuat starch solution, laminated or treated, for example, on a bonding stick, not only showed improvements in technological values such as strength, etc .; it has also become flamboyant and repulsive to vou in one go.

Example 6

Λττηή ητ · 4 ϊτ · ..τϊ> “ή 1 in v Uj A J» uU m j w flatter for the production and / use of starch p: or treating the paper of the excerpts from this find) Surface bonding on a bonding press;

Sulfamatra and starch, made as in Example 1 from native starch and 201 ammonium sulfamate, based on starch, was dissolved at a concentration of 8%. This solution showed a viscosity at 50 ° C of 50 mPa.c (Brookfield, spindle 1, 20 RPE). Using a bonding press, the solution is applied to the paper in an amount corresponding to 3¾ starch product (dry substance), based on the weight of the paper. The obtained surface glued paper not only showed improved strength and was flame resistant and water repellent.

b) Bonding, impregnation paper:

Paper st impregnates with suifamate-scroonrr. solution, made as in Example 1, in concentration, and shows a viscosity at 50 [deg.] C. 25: .i.a.fc (Drookfield, spindle 1, 2G RPl "), such that about 3" s .-; substance), based on the mass of the paper, is absorbed by the pepper. The paper thus obtained not only proved more expensive

I just have more competition was flame resistant to DZi '4102 H. 2. c) Dry paper & made js Loose coating pre.to the following j formula: 1d0 mass parts of kaoliria 12 mass 'parts of latex 2.5 masses aela suliamato · s crown (to '* m.Vi': en ke.o u? n?. '.!? ru 1) G. 7 mass d ^ la Ca-stcarnua C. 3 wt optical illuminator parts r> uva u t m ica * '<- pr c v m re bO— fc25.

'Λ. K 4. ··. .? 1 · »i r» »·

J z \ <». X <* U a »wX e or cardboard which have great properties for

This Loose Too Polar Film And Davals Are Planner Resistant: And Azai-L's Glitter is Coated So About Water Color

Dos.74194 3310 11/08/1985 _ _ _{4ύ ρ-} Ί0 5 _3/8 4

APPLICANT'S STATEMENT ON THE BEST OF THEM 'A KIND-WAY FOR THE ECONOMIC USE OF THE APPLICATION FOUND

A 20% suspension of acid-modified (degraded) starch, having a viscosity of 50 mPa.in 5% aqueous solution, measured at &lt; RTI ID = 0.0 &gt; 50 C &lt; / RTI &gt; on the basis of the dry starch substance, after which the mixture was heated to 95 ° C for 25 minutes at a pH of 4.5. The resulting sulfamate-starch solution formed, after drying, a non-flammable, water-repellent, flexible, breathable film.

Claims (8)

PATENT REQUIREMENTS: A process for the production of a flame-resistant starch product, wherein the gelatinized starch or physically or chemically modified starch which has been gelatinized reacts at a temperature of from 40 to 250 ° C with 3 to 40% by weight, based on the dry substance of the starch , one or more sulfamates selected from the group consisting of alkali, alkaline earth and ammonium sulfamates, as well as up to 80% by weight based on the total dry substance of the synthetic polymer, preferably vinyl polymers, in the presence of 30-70% by weight of water ^- based on the total mass of the reaction mixture, after which the reaction mixture is dried at a temperature of 100-200 ° C. 2. The method of claim 1, wherein the starch or physically or chemically modified starch is gelatinized in situ. Process according to claims 1-2, characterized in that calcium or ammonium sulfamate is used as the sulfamate. t The process of claims 1-3, wherein the starch or physically or chemically modified starch is reacted with 5-35, preferably 7.5-30, and in particular 10-25% by weight of sulfamate based on the dry substance of the starch. 5. The method of claim 1, wherein the reaction mixture comprises an aqueous dispersion containing a total dry matter of starch and sulfamate 30-70, preferably 35-60, and more preferably 40-55% by weight. 6. A process according to claims 1-5, wherein the chemically modified starch is degraded, acylated, etherified or oxidized starch. 7. The process of claim 1, wherein the vinyl polymer is formed in situ in aqueous dispersion by polymerization of the vinyl monomer. 8. The process of claim 7, wherein the vinyl monomer is one or more of vinyl acetate, vinyl chloride, styrene, a maleic ester, an acrylic acid ester or a methacrylic acid ester.