DE1629500A1 - A method of making expandable foamable thermoplastic resins - Google Patents

Description

• ■: & ego

"PATENT ADVOCATE:"'"■■■' _ '''^' ^-;

Dr.-in ! .H; .m RUCuHKp ^: '' ^:

^ R ", ■: ■■ 16295QQ

tr. 2 '

KanegafucM Chemical Industry Co., Ltdo, _, .- Osakaj Japan

Am a method of making ausdennbarey look tarers tiie rmoplastis rather synthetic resins. ·

...'-- "= The present invention" relates on a process for the production of vatt expandable foamable thermoplastic Kuhstharzeh (continue as ductile resins "designated), and their; subject matter of the invention is the advantageous production of: high quality porous molded body material on an industrial scale. \

The ductile resin is * like a beleannty one (homogeneous) mixture of the thermoplastic synthetic resin and the foaming agent (these are substances - which under normal conditions are liquid or gaseous and

. ■■■ '■■ """^:;"■■' ■ "" - """· ■■ ■" ■ · - ■.: To 1O9853 / 13t5

- 2 -. K 690

one of the resins to which they are added have low affinity, e.g. propane, butane, pentane, Hexane etc .., or substances that occur in an (endothermic) chemical reaction to generate gas). The porous state is achieved by heating the resin »

There are several methods of manufacture of the resin known *

Typical of many are the following

both methods: the method according to which a homogeneous dispersion system consisting of the granulated resin, the foaming agent and the medium is prepared and subjected to heat and pressure; and the process, according to which a homogeneous system from the granulated resin, a small amount of solvent (ζ.Β »toluene, benzene, etc.), the foam agent and the medium is produced and processed either with or without pressure. All these typical methods have many disadvantages · _ö

In the first described method e.g. the core of the resin beads used often becomes insufficient saturated with foaming agent »In the second process, the resin granules tend to have their surface is excessively dissolved in the solvent and many granules stick together to form a lump, consequently The size and distribution of the foam pores in the porous product that is made from it does not

uniform ,

109853/1395

690

Uniformly, if there are often caves is quite general. The time to manufacture the finished products "after this process" - It is difficult, according to these terms, to produce an elastic three-month period in a "right"
IOrm of ELa ^ tten, -stangen ,, Eoiiren ^ 5 * as «rn usm *.

. 'Each of these iSrfindung ,, the free won -the * Taesehriebenen lsi liaelxfeeilen, more than 80 e''- ^ of ^ ^ hermoplas'tlschen Eans resin and "less .als 20 fo of a or more than 2, a promoted ^ s such means, 'as aliphaliischer hydrocarbons hälogeniertfir'Kohlenwasserstoffe, woiei the boiling point .of the foaming agent should be aiiedriger as OCE ^ RVA Ohung p'unkt of MsLTzesy used zusainmengeknetet, gelatinized by heating and a -higher üsiaperatur and pressure terworfen as un-äem saturated vapor pressure d; it mousse,; with * els according to its iCemperaturc the geei is in ^ squeezed a (Jefaß ,, at which the 3> Rpt and temperature are high enough ,, that it .sich solidify can! but more difficult than in the winged or squeezed system. The oil is then cooled down and then made available. The present invention is explained in detail in the following.

.- ;. ---., - .. '. Synthetic resins of any type can be used; as long as they are -fehermorplasliic. This includes

'109853/1391 "_

. - A - K 690

e.g. vinyl chloride resins (resins made from vinyl chloride, or copolymerized resins from these and other compounds that copolymerize with it), vinyl acetate resins (Resins made from vinyl acetate or copolymerized resins made from these and such - other compounds, the copolymerize with them), resins made from methaerylic acid esters (resins made from methyl or ethereal methacrylate or

"Copolymers of one or more than two of these Compounds that copolymerize with them), resins made from acrylic acid esters (resins made from methyl and / or ethyl acrylate and copolymeric resins made from compounds that copolymerize therewith, aromatic vinyl resins (resins made from Styrene, method and / or ethyl styrene or copolymers with those compounds that copolymerize with one or with more than two of them) or olefinic Resins (resins made from ethylene, propylene and copolymers, from one or more than two of such compounds that copolymerize with them). These resins are alone or in combination of several types of ily used. Great emphasis was placed on the selection of the Types of resin, mixing ratios and other conditions, taking into account such factors as the purpose of use, the quality of the porous state, the Processability and the like will be billed

•Need to become. .

Wide rhin 109853/1 395. .- .. ......

1B29500

-5 ■■ -.-; .. Λ ;;; κ

. Next Mn is the foaming agent used an aliph.at.isch.er and / or a halogenated carbon * · hydrogen «The boiling point of this; Connections must lower than the softening point of the resin used. In the event that a mixture of more is used as two compounds, it suffices if the boiling point lower than the softening point of the resin. A mixture.". the one connection, '" contains, the boiling point of which is higher than the extension I

The resin's point of intersection is not inadmissible. Compounds that meet these requirements are, for example, ethane, propane, butane, butene, isobutylene, hexane, gyelo-hexane, pentane, methyl chloride, methylene chloride, ethylene chloride, butyl chloride, tert. -Butyl _chloride: -, "" Trichloräthain, Propylchloridj-'Dichlorpropen, Isopröpylchlorid, Bichloräthylen, propylene dichloride, dichloroethane »Pichlorpropan, ethyl bromide, Methylbrpmid, Propylbromi ^, Xthylfluorid, Äthylenfluorid, propyl fluoride ,, meth; ylfluorid, heptane, isoheptane, trichlorethylene, IsobutyleÄchlorid , amyl chloride, isobutyl, etc. These compounds can be used individually or mixed more than two of inen © warden used are less than 20 <fo these compounds with more than 80 # of resin mixed. More than $ 2 NC are too much, "For some of them, the so-called ~ occurs." Slip phenomenon during ^fl Grelierens

'-'-. and 109853/1395

■■ - 6 -; K 690

and in the subsequent squeezing, which lowers productivity. Some others soften the resin excessively and make it impossible to squeeze out. Accordingly, only less than 20% of these compounds , in particular at most 3 - 10 ° C. , can be used.

From such a stretchy synthetic apron, which contains a foaming agent whose boiling point is higher than the softening point of the one used Resin, "can be the porous body with the desired high qualities cannot be obtained because the gaseous Foam concentrate is condensed and liquefied, and the pores of the caper shrink and deform and become irregular if the gel after squeezing, Foaming and cooling still have a higher temperature than the softening temperature of the Harz has »

To accelerate the absorption of the foaming agent in the resin, can the following solvents be included in the gelling system? Methyl ethyl ketone, carbon tetrachloride, methylene chloride, toluene, acetone, benzene, etc. Less than 5 ° / u based on the weight of the resin are sufficient

ι " ^: - ■" ■■ ■

Softening is different depending on the type of resin used not inexpedient. Furthermore, the subject

Fabrics

109853/1395

_:::: ^^ '\ ■■ - - ".'. ■" -1629SlPQ.-. ".

- 7 -; K 690

Substances are added that provide cores for gas formation from the foam concentrate (such as finely powdered SiOp, calcined perlite, bentonite, mica, calcium carbonate, wood, etc.), then lubricants (ζ _o Bc zinc stearate, etc.), and Dyes; .

If one or such means are used more than two of-., The distribution and the diameter of foam pores in the porous body is ,, the i is obtained by heating the art ausdehnaren ^ jrzes, more uniform. Sometimes productivity is increased ","

The mixture of foaming agent and resin is kneaded homogeneously. Piir this corner is used the usual method, e.g. an extrusion device or a hermetically sealed boiler Stirrer. Instead of the kneading process with the help of an extrusion device or the hermetically sealed kettle can be a resin with a particular proportion; use a sciiaummittel. It is also: common; , use the resin with less than the specified amount of foam concentrate or with no foam concentrate at all.

The resin and foam concentrate are in introduced the pressing and heating system.

• It is heated according to the usual method. The temperature must be used to form a uniform

BADORiGINAL

, "-. Gels

109853/1395 ■ "" "

- a - K .690

Gels be high enough. How high it must be in the individual depends on the proportions, the nature of the components and the other conditions at). Thus, the (temperature are not generally set as an example the temperature of 150-210 ⁰ C is given for a mixture of 92 $ polystyrene and 8 fi butane;. 190-250 and ⁰ ß for a mixture of 97 ■ # acrylonitrile • Butadiene-styrene as a graft resin and / 3 ^ pentane.

After that, the system is heated in order for it

ψ - ■■■■.

gels and is then under a pressure that is above the saturated vapor pressure, as a function of temperature d, it is the foam agent concerned. presses .. The foam is completely liquefied and uniformly distributed within the gel. Because the pressure on the type of resin and foaming agent and the Depending on other conditions, it cannot be determined generally. Usually a print of 50-150 kg / cm preferred. If only one foam concentrate

If a gaseous substance is used or such a substance is used in conjunction with a liquid substance, the gas is not liquefied below the saturated vapor pressure depending on the temperature and is therefore difficult to distribute in the resin gel.

The'gel is in a bar or in a compression vessel where the pressure is high enough

around 1 G9S5 3/1395 "

- 9 -: _ E 690

to prevent the resin from foaming, but below the PreMrucfces in the yelling system the ambient temperature. Then the squeezed out gel at the opening of the nozzle is cooled below its softening point. By .this cooling down the gel begins to look to solidify quickly by itself forms a thin layer on the surface, then the inside solidifies. Because of this, the Foam concentrate that has been uniformly distributed in the resin, | Any inevitable in the resin Coolant, either gas or liquid, is applicable. Among them, water is very effective and advantageous.

If the pressure is less than is needed to suppress foaming, then the foaming agent expands and escapes from the hara. As a result one obtains a dehnbarea resin whose elasticity is less than desired * The applied pressure ι not kajin are generally fixed, because ei ^ iängt from the resin and from the foaming agent. For example, a pressure of about 10-13 kg / cm ^ is applied when foaming polystyrene with butane. The pressure is applied to the ffefiäß by conventional methods. For example, an inert gas (nitrogen, carbon dioxide, etc.) can be introduced, or one ^ generates ^^ a pressure with the help of water * -

1Q9853 / 13S5 "

That

- 10 - K 690.

The desired product is manufactured according to the usual methods, for example, by opening the opening sets up the press in such a way that certain shapes are created, e.g. fiber jars, ribbons, plates., round bars, square bars, etc. Or can be obtained by putting the product inside or cut up outside the vessel.

In this way, a ductile resin with a certain, desired shape or Shape, grain size and ductility can be obtained.

Some of the functions and effects that achieved by this invention are explained below!

I) -The time it takes for the Resin is needed is very short.

As already described, the usual chemical processes take a long time, whereas this invention based on the pressing method takes a very short time.

2) Granules of a dellable resin that not used individually to produce porous bodies i.e. resins with a low foaming agent content or very fine resin powder can be used as Starting material can be used. Because even very fine resin can be processed using the extrusion process

109853/1395,

IllllflO

become, and the desired one = J * esha | 1; iäg @ Aufsaiip.u | nens in. the heat-foamable resin can be made by etching Zufujix yöii ßelia? Immit1; eJL err ^ gLjcJit deserve.

5) iDas bestipiatje 4 ^ toii> are --- Ipzw., .ScUßmi ß resin fearui in. The desired, and someiiei% lipjien mang ^ stellib we3Pd; en. . . . .

The resin iet .natürlix li lBicht frerforml> ar ieitlißhen to a}, 3 ai) le1;? ^ _S? Ptangen, ilatiben, etc. By heating, porous bodies are obtained. d ^ e ge ~ |

are exactly the same size, whose! " Durchuiesser and lTeiit ^ i | ung ha ¥ eji, which have a good surface, and which - furthermore, have a good size ratio to the elastic resin used.

This i $ t possible because of the resin and that The building materials were kneaded uniformly and that Show agent homogeneously contained in the expandable resin is"

"4") The decrease in extensibility ßfoambarkeit of the resin obtained over time is very little =

Even such grains of deniable resin, The microporous grains are (i.e., kprititps resin, that one ciurch Suspensi.onspoi.ymerisation des has received) know as starting material v will.

". ■ ■ '^ In

109: 8 53/131 $ '~

~ 12 - .K 690

- In one of these; Harzkorh escapes that Foam compound to the outside through the smallest hole in the Resin and. consequently, the extensibility / foamability within a certain time. This inclination is "More noticeable in the case of gaseous foaming agents with a low boiling point. - - - ■

Nevertheless, the speed with which the "foaming agent contained escapes, so small that the decrease in the W extensibility within the time very.

is low because the resulting product is a coating layer is formed by the gelation, after cooling and solidifying under pressure and temperature at which the foaming agent enclosed · can not foam, _r, and further at the surface.

The embodiments are shown below of the present invention demonstrated:

t example 1

■■. - -, '.-'- A mixture of 100 * weight st eilen styrene-.

- Resin and 2 parts by weight of diet omenerde (Tylersieb with 250 mesh) was gelled and with a 90 singleshaft-'2 stages type — Auspreßv ^ orriclitmag pressed.

. Initially, the mixture was used with a throughput of 70 kg / h. The mixture was then gelled by bringing the temperature in the cylinder to 152 ^° C. through the surrounding steam and operating the first screw.

BAD QfIIQINAl

1098 53/1 39 5

Under

- 13 - ;; K 690

Under pressure, 8 weight points of butane would be in the gel is introduced and the mixture is kneaded by operating the second screw. te an internal pressure of 57 »5 kg / cm. Everything was butane ■ liquefied and dispersed homogeneously in the resin

In the next phase the gel was through a nozzle (20 holes, diameter of each hole 2.5 mm) pressed into a vessel in which a pressure of 13 kg / cm prevailed, so that when the second screw |

the pressure in the system rose to 70 kg / cm. This vessel

^{1 ;} filled ■ .'V'-. was with circulating water he /; so that a temperature of 50 ^° C. was _{constantly maintained o} The pressed gel was cooled and solidified by contact with the water, and 20 threads were formed.

There was a rotating one at the exit of the nozzle Knife attached so that the solid threads in pieces about 1 mm long.

These cut bits were made out taken out of the jar and dried. There were 107 parts by weight of granulated expandable foamable Resin obtained.

From these granules is obtained by heating at 105 G ⁰ within 10 minutes of a porous body from the volume 700 eo / lO g / aufwiese the pores of which a good distribution and uniform Durchraesser & and a smooth surface had. '

109853/1395

- U - - K 690

Example 2

A mixture of 100 parts by weight of a copolymer of acrylonitrile and styrene, 2 parts by weight of diatomaceous earth (Tyler's sieve with 300 mesh) and 8 Parts by weight of pentane were allowed to gel and with Using a hermetically sealed kettle equipped with a stirrer at an internal temperature of 120 C pressed out.

First nitrogen was introduced under a pressure of 60 kg / cm into the gas space of the boiler, and the gel was pressed through the holes of the nozzle (25 holes, diameter of each hole 2 mm) into a vessel to solidify. so that a pressure of 6 kg / cm and a temperature of 5O ⁰ C constantly prevailed. The squeezed gel was cooled and solidified on contact with the water, and 25 strands of the resin were formed. These strands were withdrawn from the vessel through holes prepared for this purpose. Fibrous gland packings were placed in these holes to prevent the escape of water. The strands of the resin are cut into pieces about 2 mm long by a cutting machine «

. These cut pieces were 1 minute examples 40 ⁰ C dried to give 108 so

8AD

. Weight parts

109853/1395 ~

("' ■. ■ "■■■ - 15 - K 690

Certainly good elastic granules of resin o - ■

Benan'deit iaan these grains as in example 1, you get porous bodies with a volume of 750 ec / 10 g, whose pores have a uniform diameter '. and have good distribution and have a smooth surface.

Example 5 ^: ■ _% -

A semicircle of 100 parts _by weight of one

highly impact-resistant resin (styrene-butadiene Pröpfcopolyme- * f ren) and 5 elected parts ierlit was left geliereh 'and with the sowing speed of 150 kg / h' with the help of a (single-shaft 2-stage type 115 0) Press approved * ■: ■ -. ■.

During this process, 5 weight points of pentane were introduced into the second throughput. The mixture was kneaded at 170 ^Q G and düröh a IKise 0.25 χ 670 mm in: pressing a "GefHß" that with a pressure of 10 lcg / em loaded warv Diireh Besprü-, hen with water, the resulting Ppiätte a The temperature is kept below 5 ^ ¹ Q and then removed from the vessel. '·. / /

This plate, which was attached to the right and left, was heated in a vacuum 3urOh infrared heater, and a uniformly expanded, well-shaped body with a specific gravity of 0.075 was obtained ^;

example A.

109 853/13 9 5 ^v V ^:; _ολ

BATH ORIGINAL

- 16 - E 690

Example 4 . .

A mixture of 100 parts by weight

granulated methyl methacrylate resin, .2 parts by weight Perlite and 3 parts by weight of methyl ethyl ketone was allowed to gel and hermetically using a closed boiler (capacity 200 l), the was provided with a stirrer, squeezed out.

First, the mixture was charged through a port in the boiler, gene leads and thoroughly kneaded with stirring ο should G-emic allowed to gel ,, wherein a temperature was maintained from 115 ⁰ C by injected steam. 7 parts by weight of butane was introduced into the gel under pressure, and the mixture was stirred, kneaded and gelled.

In the upper gas space of the boiler was

2 nitrogen introduced to a pressure of 70 kg / cm to produce and the gel was through, a nozzle (30 holes, Diameter of each hole 2 mm) into a vessel

■ O- -

pressed, the internal pressure of which was 15 kg / cm The opening of the nozzle to the vessel was equipped with a cooling and cutting device.

The squeezed gel was cooled and solidified by the water sprayed over it then cut into 2 mm long pieces.

These

109 853/13 9 5

BAD OHlGlNAL

- 17-. K 690

These tablets were removed from the jar taken out In this way, 105 parts by weight of such resin tablets were obtained. These were treated as in Example 1, and porous' Bodies stretched to 55occ / lQ g, their Cells of uniform diameter and good distribution showed, and the surface of which was smoothν

Example 5 , V: ·.

A mixture of 100 parts by weight of one ~ "

Copolymers of vinyl chloride and vinylacetr.t., 2 parts by weight of calcined pearlite, 3 parts by weight of methyl ethyl ketone and 2.5 parts by weight of dioetyiphthalate were gelled; sen and pressed with the help of a 90 0 single-shaft two stage_screw type pressing device ».

This mixture was filled with a saturation fluid of 60 kg / h from a hopper filled in, just press the first screw. |

the mixture should gel «The internal temperature of 125 ° iJ was achieved by heating the cylinder with steam achieved ο The gel was transferred to the second stage in which 8 parts by weight of pentane were introduced under pressure with the pump and the gel at a ' Internal pressure of 20 kg / cm was kneaded.

109853/1395

BATH

ι υ c ν? -j Kj \ j

■ - 18 - κ 6yo,

At that time the pentane did not flow in the system to the starting resin aurliek because the gel of the first Stage prevented it from becoming uniform in it distributed.

The pressure of the system was then increased to 60 kg / cm by using the second stage and the gel was pressed into the pressure vessel through the holes in the nozzle (18 holes, diameter of each hole 2.5 mm). This vessel was rigidly under the pressure of 7 kg / cm " -.

A cooling device was attached to the end of the nozzle. The pressed gel was cooled by water from the spray device and solidified into 18 resin strands. These strands were taken out of the vessel and drawn into holes prepared for this purpose, which were connected in a straight line to those of the nozzle. These holes had rubber pegs. sealed against air ingress »Outside aes. In the vessel, the resin strands were cut into pieces about 2 mm long using a rotating cutter. These tablets were dried for 1 minute at 40 ^° C. and 105 parts by weight of an expandable resin were obtained in this way

When heated, these tablets 10 minutes 105 ⁰ C, -SO obtained shaped porous body, dip

109853/139 5 ... , _r

BAD OBSGSNAL

- - 19 - .- K 690

- have stretched to 400 cc / 10 * g, the pores of which are uniform in diameter and distribution and that have smooth surfaces. . '■ -.- .. ■■■ · "- .." ·

'Example ' 6. "'■." - .. "". ■ ".

^£ '.. A mixture of 100 parts by weight st eil en styrene resin and 3 Sewiciitsteilen Cäiciumearbohat was prepared from a 90 φ double-shaft 2-stage pressing machine pressed ■ :. '■■■ -' -

First, the mixture in the ers _(was ten. ■ "stage at 145 ⁰ C allowed to gel. The resulting gel was transferred to the second stage. A mixture of 7 Gewiehtsteilen butane and 1 Gewiehtsteil styrene was added to this stage through an opening, and.

ο ■■■ "/ - 2 -

The gel was kneaded at 152 ° C. and an internal pressure of 50 kg / cm. Through a rectangular diameter (7 x 42 mm) attached to the end of this part, the product was poured into a solidifying vessel at a throughput rate of 100 kg / h pressed, in which see stick- | fabric was under the pressure of 13 kg / cm. The extruded product was cooled to 5 NC C by passing it continuously sprayed with Wasiäer 48 ⁰ G., and was Hommen in a collecting vessel. On: these catfish were obtained 108 parts by weight of expandable resin in the form of plates.

These plates were cut into 42 mm long pieces.

■■■ "· - Pi, ^eSie '- 1 09853/1335 BAD

- 20 -. K 690

These pieces were placed in a vessel measuring 126 126 χ 21 mm (internal dimension), the wall of which with many fine holes was «This vessel was heated in an autoclave * Bs became a beautiful shaped porous body with the specific Weight O »037 preserved.

V at entitlement

9853/1395

Claims (1)

Eatentaiis saying A method for producing a stretchable, foamable thermoplastic resin, characterized in that; is more than 80 (Jew - $ a thermoplastic resin and less than 20 wt .. - $> one or more than two kinds, such Sehäummittels such Bo ^ aliphatic and Kohlenwaöserstoffe. halogenated hydrocarbons .veran.seht where If the boiling point of this foaming agent is lower than the softening point of the processed resin, that the mixture is heated under higher pressure than the saturated vapor pressure of this foaming agent, which depends on the temperature of the old man, that the. "" The resulting oil is pressed into a vessel whose pressure and temperature are lower than in the gelation system, but sufficient to prevent foaming of the foaming agent, that this gel is solidified and shaped inside or outside the vessel, and that it is in a desired shape is brought. Dr Pa-ZBr.
K 690 109 853/1395