DE2018532A1 - Process for the production of foams based on vinyl chloride polymers (I) - Google Patents

Description

concerning

Process for the production of foams on the basis

of vinyl chloride polymers (I)

The invention relates to a method of manufacture of both soft and hard cellular products based on vinyl chloride polymers, as well as those after this Process manufactured products themselves.

It is well known, foams made from polyvinyl chloride by mixing polyvinyl chloride with certain organic substances, such as biuret, and the mixture then subjected to a heat treatment. The organic substances decompose and cause the expansion of the Polyvinyl chloride. It is also known to add oxalic acid and urea to polyvinyl chloride and then to heat it. In all of these reactions, however, only a weak evolution of gas occurs which does not allow foams with a low density to be obtained.

Sodium carbonate was already used as a friction agent an acid such as tartaric acid. It is also

known,

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the foaming of polyvinyl chloride with sodium borohydride to effect that, under the action of an acid, releases hydrogen, a flammable and, above all, diffusing gas.

However, these propellants can only be used with care and react with each other even at room temperature, so that foaming can only be controlled with difficulty.

It also became urea oxalate, which decomposes under heat proposed as a propellant for polyvinyl chloride, but this substance must be prepared beforehand. As a matter of fact the results obtained by adding the above-mentioned mixture of oxalic acid and urea to polyvinyl chloride can be obtained do not compare with the results obtained by adding previously prepared urea oxalate.

The invention is based on the object of avoiding the disadvantages of the known methods and the production of To allow cellular products with a low tree weight based on vinyl chloride polymers by using as blowing agents an easy-to-use chemical system is used, the decomposition products of which are non-flammable and which relate to can use all possibilities of processing the polymer.

According to the invention, at least one vinyl chloride polymer is included A propellant is added which is composed of at least one nitrogen derivative of carbonic acid and at least one unsaturated Carboxylic acid containing 3 to 12 carbon atoms; the carboxylic acid is selected from the group of aliphatic carboxylic acids with one starting from the α- or ß-carbon atom Double bond or triple bond, optionally substituted with at least one halogen atom, a lower alkyl group, a phenyl or phenoxy group and from the group of optionally with at least one alkyl group or a halogen atom substituted aryl acids selected; the mixture becomes

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- 3 'gelled, shaped and foamed.

t *

As vinyl chloride polymer in the present description

Exercise all homopolymers, copolymers and / or post-chlorinated Polymers of vinyl chloride, »mixed with each other or with other compatible polymers, such as polypropylene, polyethylene, Polystyrene, polyurethane, vinyl acetate-ethylene copolymer and acrylonitrile-butadiene-styrene copolymer understood.

Will blends of vinyl chloride polymers be compatible with others If polymers are used, the proportion of vinyl chloride polymer should make up 50 to 99% by weight of the mixture.

If a vinyl chloride copolymer is used, this can contain at least 50% by weight of vinyl chloride units and units contain at least one further comonomer; as comonomers come vinyl esters, such as vinyl acetate, alkyl acrylates and Alky! Methacrylate, fumaric acid ester, maleic acid ester, chlorofumaric acid ester, Chloromaleic acid ester, alkyl vinyl ether, vinylidene chloride, vinyl pyridine, ethylene, propylene, acrylonitrile and vinyl alcohol in question.

The copolymer can also be a grafted homopolymer or copolymer of vinyl chloride, which is mainly made with butadiene and Acrylonitrile, butadiene and alkyl methacrylate and / or alkyl acrylate, is grafted with butadiene, an alkyl acrylate, styrene and a crosslinking agent such as divinylbenzene.

For the production of the polymers and copolymers of vinyl chloride all known processes can be used: bulk polymerisation, suspension polymerisation, polymerisation in fine suspension (or microsuspension) or emulsion polymerization.

The post-chlorinated (perchlorinated) vinyl chloride polymers are also produced by any known method,

* single, _ 4 _

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> , in particular according to the method described in French patent specification no. 1 439 877 and its addendum no. 89 193.

The nitrogen derivative of carbonic acid, which is a component of the propellant mixture used according to the invention corresponds to the general formula:

R ²

R ¹ - NH - C -

wherein X is an oxygen or sulfur atom or the imino

1
group means, R hydrogen, an alkyl group with less than 6 carbon atoms, an acyl group with less than 5 carbon atoms or the optionally substituted

ρ
Carbamyl group denotes, R denotes hydrogen or an alkyl group with less than 6 carbon atoms and Br denotes hydrogen, an alkyl group with less than 6 carbon atoms, an acyl group with less than 5 carbon atoms, an optionally substituted carbamyl group or a saturated aliphatic ester group with less than 6 carbon atoms.

If the carbamyl groups are substituted, the substituents are alkyl groups with fewer than 4 carbon atoms.

The compounds that correspond to the above formula include urea, biuret, thiourea, acetylurea, diacetylurea, triuret, guanidine, lower alkylallophanates, lower alkylcarbamylallophanates, N-methyl-N ¹ -acetylurea and N-methyl-N ¹ , N ' -dimethylurea.

The optionally substituted unsaturated aliphatic acids and optionally substituted ones used in the propellant Aryl acids are the monocarboxylic acids, dicarboxylic

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acids and the existing anhydrides of these acids, harvesting 3 to 12, preferably 3 to 6 carbon atoms.

As examples of this definition corresponding monocarboxylic acids, acrylic acid, crotonic acid, pentenoic acid, methacrylic acid, Angelica be acid, Teracrylsäure, cinnamic acid, 2-phenoxy-acrylic acid _r 2-phenoxy-3-buten-oic acid 1-, propargylic acid, tetrolic acid, heptyne-carboxylic acid, Phenylpropargylic acid, 3-butynic acid, benzoic acid, toluic acid and parachlorobenzoic acid.

Examples of dicarboxylic acids are maleic acid, fumaric acid, Glutaconic acid, citraconic acid, itaconic acid, 3-hexene-1,6-di- acid, butynedioic acid, PBthalic acid and naphtholic acid.

The main anhydrides are maleic anhydride, glutaconic anhydride, Citraconic anhydride and phthalic anhydride in question.

The molar ratio of unsaturated to be maintained according to the invention aliphatic carboxylic acid and / or aryl carboxylic acid to nitrogen derivative of carbonic acid depends on the respective The nature of the components of the propellant mixture and is 0.2 to 2, preferably 0.4 to 1.5.

According to the invention, at least one of the unsaturated acids mentioned is combined with at least one nitrogen derivative Carbonic acid combined to form a propellant mixture, its Decomposition temperature is equal to or higher than the gel temperature of vinyl chloride polymer.

The propellant mixture is the vinyl chloride polymer in an amount ratio of 2 to 100 wt .- 56, preferably from 2 to 40 wt .- # added.

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Depending on whether a rigid foam or a more or less soft, cellular product is to be produced the vinyl chloride polymer has different amounts of plasticizer (n) added, as are commonly used in the processing of vinyl chloride polymers. In question butyl benzyl phthalate, dioctyl phthalate, Dibutyl phthalate, dicapryl phthalate, dinonyl phthalate; DiactyI-adipat, Didecyl adipate; Dibutyl sebacate, dioctyl sebacate; Tricresyl phosphate, trioctyl phosphate, trixylyl phosphate, Octyl diphenyl phosphate; chlorinated paraffins; epoxidized oils and esters; polymeric plasticizers, such as polyester Adipic acid or sebacic acid and finally the at Room temperature solid plasticizers, such as polymethyl acrylate and polymethyl methacrylate, polyethyl acrylate and polyethyl methacrylate, Polybutyl acrylate and polybutyl methacrylate and fatty alcohols.

The plasticizers are obtained in amounts from 0 to 150% by weight on the vinyl chloride polymer, added, as appropriate Degree of softness of the cellular product.

You can also use crosslinkable plasticizers, such as Diallyl phthalate, ethylene glycol mono- or dimethacrylate, Propylene glycol mono- or dimethacrylates and unsaturated Polyesters which, after crosslinking, give cellular products whose heat resistance is noticeably improved.

The crosslinkable plasticizers are used in amounts from 0 to 25 % By weight, based on the vinyl chloride polymer, added.

The vinyl chloride polymer can also be customary Stabilizers and lubricants are added.

The following stabilizers are mentioned: The neutral or basic lead salts, namely carbonates, sulfates, phosphites, silicates and stearates; the calcium, cadmium, barium, zinc, ♦ d. h » dimensional stability in aer ^ araae - 7 -

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Lithium »and strontium salts, especially the stearates, Octoates and laurates; the tin compounds and that Dilaurates and dimaleates of dibutyltin, dioctyltin, thiooctyltin and thiobutyl tin; Zinc oxide and / or urea and / or biuret (French patent 1,475,865). These Stabilizers are obtained in amounts from 0.2 to 8% by weight on the vinyl chloride polymer.

The nature and amount of the lubricant used depend on the chosen processing method. Examples are: stearic acid, the neutral ones or basic lead stearates, ethyl palmitate, paraffin waxes, Ester waxes; the lubricants are used in amounts of 0.1 to% by weight, based on the vinyl chloride polymer.

In some cases it may be useful to add vinyl chloride polymers Incorporate additives such as are usually used when processing polyvinyl chloride. These are, for example, fillers, nucleating agents, structure regulators, crosslinking agents and dyes.

Fillers such as chalk, kaolin, silica and carbon are sometimes desirable, but their amount should not exceed 50%, preferably less than 20%, by weight of the vinyl chloride polymer make out.

Nucleating agents are not absolutely necessary, but can be added will; Azo compounds such as azodicarbonamide, isopropyl azoformate, barium azodicarboxylate, for example, are suitable or carbon black in amounts of 0.05 to 1.5% by weight, based on on the vinyl chloride polymer.

The structure regulators are mainly products of the type condensation products of ethylene oxide on fatty acid chains and are used in amounts of 0.05 to 1% by weight, based on the vinyl chloride polymer.

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As a crosslinking agent all come with polyvinyl chloride ' and vinyl chloride polymers compatible crosslinking agents, for example an ethylene-vinyl acetate copolymer, a graft polymer of butadiene and acrylonitrile on polyvinyl chloride and the crosslinkable plasticizers listed above. These crosslinking agents are used in amounts of 0 to 25% by weight, based on the vinyl chloride polymer used. The networking takes place chemically by any known method. It can also be brought about by radiation.

The various components are mixed, gelled, shaped and foamed in the course of the usual processing methods, such as compression molding, injection molding, extrusion molding, calendering and coating, with the individual operations be carried out separately from one another or combined with one another {for example, gelling and foaming, gelling and compression molding or compression molding and foaming combined.

The propellant mixture according to the invention can be the vinyl chloride polymer be added after gelling.

In compression molding, emulsion polymerization is preferably used vinyl chloride polymer prepared or polymerized in microsuspension is used. Receives after mixing a paste which is then shaped and pressed under conditions of temperature and time which allow gelation. The he. After cooling and demolding, the molded body is held either with hot air or with steam, in a hot Water bath or a hot oil bath or by IR irradiation or foamed by high frequency or ultra high frequency. For the Processing by extrusion, injection molding and calendering is carried out through bulk polymerisation, suspension polymerisation, Polymerization in microsuspension or emulsion polymerization produced vinyl chloride polymer is used. The polymer can have a high viscosity number if a small

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aäHlsfe errvainscjjfe ist.i will, a Harts.chaum-so? ssäill dffe? V4isk0s & ta * s3iaJüP be low.

Ge »a & Gfc in. A- Sfecangpresae? uadi dl & u- Stean ^ resident: becomes thin as indicated

^ wirjä the mixture: an ^ indel press or BaiLih & npxes® & abandoned ,, the gelled product is in one; Börjaj sprites poured and the after cooling and EntfiorÄßn e ^ haliiene molding foamed in the manner indicated. Foaming; can also be done directly in the Eorm.

During calendering, the constituents are mixed with one another, gelled: and formed from them into foils or plates produced and 'these in the specified manner as well fail ·.

Processing is done by coating with a plastisol a by emulsion polymerization or polymerization in Microsuspension made vinyl chloride polymer is used. All ingredients are mixed together to form a paste. Bas. ßeüJieinen and foaming takes place when going through The SteceAi3iüi »machine>, Kir the coating can also be powder-like $ Geaiische will apply} in this case a dujcßJt! Bionic or bulk polymerization

used.

The exfiäend1in§sg.päßi preserved cellular products or foam s \ ta $$ E & f show! g ^ & sciiltossene and / or open cells, depending on the de-c Εβ · ζ »|| Μτ _νί dtemi chosen processing method and the conditions»; at"; Foaming. The cell diameters and theirs depend on: the same parameters.

: According to the invention, very different cellular . - 10 -

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Manufacture products, for example:

thin (<5 wt) _. Soft foam: with a high density (> 0.2 g / cm ³ ),

thick (5 to 100 mm) WeicliBchaumatoffe low density (<0 _r 2 g / cm ^_5);

thick (5 to 100 mm) foam with all sorts. Volume weights (0.025 to 0.85 g / cmr). ».

The cellular products according to the invention based on Vinyl chloride polymers are found in various fields Application: as heat and / or sound insulation, connecting parts, artificial leather, underlays for floor coverings, upholstery, in the construction industry, in the furniture industry and as Packaging materials.

The invention will now be elucidated by means of the following examples explained:

Example 1

Were placed in a Plästisol mixer at room temperature :

200 g polyvinyl chloride, produced by emulsion polymerization, viscosity number 180, measured according to the French standard T 51 0.15, 32.4 g urea,
30.4 g. Maleic acid and
2 g zinc oxide.

Mixing was carried out for 15 minutes, after which 70 g of butyl benzyl phthalate were added added and mixed for a further 10 min. there has been a putty-like viscous paste obtained

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This paste was brought into a cylindrical shape with an internal diameter of 7 cm and a height of 1 cm and then ^{pressed for 50 minutes at 180 °} C. and a pressure of 100 bar. It was then cooled to room temperature and kept under the same pressure for 20 minutes. ·

The mold was then removed from the mold and the molded body was left to rest for 20 minutes before it was expanded in an oven at 120 ^° C. for 15 minutes.

A soft foam was obtained, the density of which was 0.47 g / cm *.

Example 2

The procedure was as in Example 1, but with 30.4 g of fumaric acid instead of maleic acid. The obtained pliable or soft foam had a density of 0.2 g / cm3.

Examples 3 to 5

The procedure was as in Example 1, but the maleic acid replaced by various monocarboxylic acids in appropriate amounts.

The monocarboxylic acids, their amounts and the test results are summarized in Table 1 below.

TABEL Art weight
G 1 Foam Procure
Ness example acid Acrylic acid
Crotonic acid
Benzoic acid 37.8
46
65.6 Tree weight
g / cm3 soft
H
very soft
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0.30
0.25 3
4th
5

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- 12 examples 6 and 7

It was according to Example 1, but with anhydrides in the same Amount worked instead of maleic acid. The reaction conditions and the results are as follows Table 2 summarized.

! TABLE 2

example Anhydrides Art weight
G Foam Procure
Ness Maleic acid
anhydride
Phthalic acid
anhydride
ie 1 8 25.6
• 58.8 Space
weight
g / cm * soft ■
Il 6th
7th
B ice ρ 0.27
0.43

The mixture was mixed for 10 minutes at room temperature in a high-speed mixer

2000 g copolymer of vinyl chloride and vinyl acetate, containing 15% vinyl acetate units, produced by suspension polymerization, with viscosity number 60 according to the French standard T 51-013, 320 g fumaric acid,
300 g biuret and
60 g lead stearate; (dibasic)

the mixture was fed into an extruder, whose jacket was heated at three different locations: at the filling opening at 110 ⁰ C, in the middle part to 120 ⁰ C and at the mouthpiece to 140 ⁰ C. In the mouthpiece a head portion and a die were set up, which were heated to 140 or 120 ^{° C.}

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The output of the extruder was 3.5 kg / h.

The sheet was foamed pin 15 in an oven "at 20O ⁰ C. It has been such a rigid foam with density 0.06 g / cnr obtained.

Example 9

It was according to Example 8, but with 550 g of acetylurea worked instead of 300 g biuret.

A rigid foam with a density of 0.07 g / cnr was obtained.

Example 10

The following were mixed up:

1000 g copolymer of vinyl chloride and vinyl acetate, containing 15% vinyl acetate units, obtained by suspension polymerization, with viscosity number 60 (French standard T 51-013),
30 g lead sulfate (tribasic) and 3 g lead stearate. (dibasic).

The mixture was mixed on a roller mixer at 115 ° C for 10 minutes kneaded until gelled. Then kneading was continued and a mixture of 150 g of urea and 160 g of fumaric acid was added. It was kneaded for a further 10 minutes.

The mass was processed on foils, which can be cooled on a flat surface.
Let foam for 15 minutes.

cool flat surface and then in the oven at 200 ⁰ C during

A rigid foam with a density of 0.06 g / cinr was obtained ^; keep.

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Example 11

The procedure was as in Example 10, but only 75 6 Urea and 80 g of fumaric acid are used. A rigid foam with a density of 0.05 g / cm * was obtained

B e i s ρ ie I 12

The following were kneaded for 10 minutes:

600 g copolymer of vinyl chloride and vinyl acetate, containing 3% vinyl acetate, obtained by emulsion polymerization, with viscosity number 130 (French standard T 51-013),
30 g urea,
30 g of fumaric acid and

9 grams of a mixture of cadmium octoate and zinc octoate were added 450 g of butyl benzyl phthalate

added and kneaded for a further 30 min.

The mixture was then crushed and then degassed. The plastisol obtained therefrom was painted onto a paper film, gelled and expanded for ^{3 min at 200 ° C. in a tunnel oven.}

A paper with a soft foam layer was obtained, the density of which was 0.35 g / cm.

Example 13
The following were mixed:

500 g polyvinyl chloride, obtained by bulk polymerization, viscosity number 60 (French standard T 51-013) 1,500 g copolymer of vinyl chloride and vinyl acetate, containing 15 % vinyl acetate units, produced by suspension polymerization, viscosity number 60 (French

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French standard T 51-013),

162 g urea, ·. .

152 g fumaric acid,

50 g dioctyl phthalate,

30 g lead stearate (dibasic) and

10 g lead phosphite (d! Basic)

The mixture was prepared by kneading by a roll mill for 10 minutes at 110 ⁰ C gelled.

The mass was processed on foils, which were then cooled on a flat surface and in the oven at 180 ° C for 15 minutes foamed up.

A rigid foam with a density of 0.2 g / cm3 was obtained.

example

The following were mixed:

1000 g copolymer of vinyl chloride and vinyl acetate, containing 15% vinyl acetate units, produced by suspension polymerization, viscosity number 60 (French standard T 51-013), 160 g urea, '
150 g fumaric acid,
30 g lead sulfate (tribasic)

3 g lead stearate (dibasic)
50 g ethylene glycol dimethacrylate and 1 g cumene hydroperoxide.

The mixture was kneaded in a roller mixer at 110 ° C. for 10 minutes to gel. Then the mass was on foils λ works that you can cool down on a flat surface and

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kneaded at 110 ° C. The mass was then put on foils

Len thereon minutes left to foam at 200 ⁰ C in the oven during the 15th

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A rigid foam with a density of 0.1 g / cm was obtained.

The heat resistance »d. H. i'Ormbest & nuigkeit in der V »'ärme, wurae with a test specimen 40 mm 40 ram χ 20 mm under a

Load of 250 g / cm was determined, the temperature was measured at which the thickness of the test body had decreased by 5 ^c / . This temperature was 85 Q.

The same experiment was used for comparison, but without ethylene glycol methacrylate and carried out without cumene hydroperoxide. The rigid foam obtained had a haum weight of 0.1 g / cm, its heat resistance was only 75 ° 0.

PATKKTANuPRÜCHE ί

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Claims (10)

Claims 1. Process for the production of foams on the base of vinyl chloride polymers using a nitrogen derivative of carbonic acid and a organic acid-containing propellant mixture, the vinyl chloride polymer being used in a manner known per se with the propellant and optionally plasticizers, stabilizers and other customary additives mixed, the mixture gels, deforms and foams, characterized in that one Propellant mixture used that a) at least one nitrogen derivative of carbonic acid of the formula R ¹ -HH-ON χ ν contains, wherein X is an oxygen or sulfur atom or the imino group means R is a hydrogen atom, an alkyl group with less than 6 carbon atoms, an acyl group with fewer than 5 carbon atoms or optionally with Alkyl groups with less than 4 carbon atoms substituted The carbamyl group means R is a hydrogen atom or an alkyl group with fewer than 6 carbon atoms and R ^{5 is} a hydrogen atom, an alkyl group with fewer than 6 carbon atoms, an acyl group with fewer than 5 carbon atoms, one which is optionally substituted by alkyl groups with fewer than 4 carbon atoms Carbamy group! or is a saturated aliphatic Estergruppe with less than 6 carbon atoms and b) have at least one 3 to 12 carbon atoms- ever The unsaturated carboxylic acid contains an aliphatic carboxylic acid with a double or triple bond in the C ^ i ß- or ß, Of -position _/ optionally substituted with at least one halogen atom, a lower alkyl group, phenyl or phenoxy group and / or an optionally alkyl - Or halogen-substituted aryl acid or a corresponding anhydride. 2. The method according to claim 1, characterized in that the nitrogen derivative of carbonic acid is urea, biuret, thiourea, acetylurea, diacetylurea, triuret, guanidine, lower alkylallophanates, lower alkylcarbaaylallophanates, N-methyl-N'-acetylurea or N-methyl -N ¹ , N'-dimethylurea used. 3. The method according to claim 1 or 2, characterized in that the unsaturated acid a dicarboxylic acid, in particular maleic acid and / or fumaric acid, is used. 4. The method according to claim 1 or 2, characterized in that the unsaturated acid a monocarboxylic acid, especially acrylic acid, crotons ". ^ e and / or benzoic acid is used. 5. The method according to claim 1 or 2, characterized in that the anhydride is maleic anhydride and / or phthalic anhydride. 6. The method according to claim 1 to 5, characterized in that a molar ratio of unsaturated acid to nitrogen derivative of carbonic acid of 0.2 to 2, preferably 0.4 to 1.5 is maintained. 00 $ # ^{46/177 $ '- BAD 0RiG! N} * L -S- 1A-37 602 7. The method according to claim 1 to 6, characterized in that the propellant mixture is used in an amount of 2 to 100 wt. ^, Preferably from 2 to 40 wt .- ^ ₁ based on the vinyl chloride polymer. 8. The method according to claim 1 to 7, characterized in that the vinyl chloride polymer is used a homopolymer, copolymer, post-chlorinated polymer or mixtures of homopolymers, copolymers and post-chlorinated Polymers used with each other or with other compatible polymers. 9. The method according to claim 8, characterized in that one is a vinyl chloride copolymer used which contains at least 50 wt .- # vinyl chloride units, 10. The method according to claim 8 or 9, characterized in that mixtures of vinyl chloride polymers and other compatible polymers are used which contain 50 to 99 wt. -4> vinyl chloride polymer, based on the total mixture. 0098A6 / 1775