DE1911804A1 - Mixed material preparation for shaping into molded parts and process for their production - Google Patents

Description

Mixture preparation for shaping into molded parts and process for their production

The invention relates to a mixed material preparation for molding in molded parts and a process for their production.

Field of application of the invention are injection molded and extruder molded parts, in particular novel "preparations for shaping into such molded parts. Such preparations-im essentially of two thermoplastic polymers, one of which at least partially forms a graft polymer, as well as from a cellulosic, high polymer component in particle form, which is impregnated with thermoplastic polymers.

The technique of impregnating a cellulosic, high polymer Substance in particular of wood, with a polymerizable vinyl compound and the polymerization within the Wood to produce a composite (wood-plastic composite) between the wood and the polymer from this polymerizable vinyl compound is known. Normally are such wood-plastic composites using wood-based materials in a self-supporting or component-like manner Form produced, for example using plates, strips, strips and post-like or rod-like parts; such materials are used where the good physical properties and the external appearance of the wood are used should be.

In contrast to the rapidly increasing costs of quality

909848/1126

191T8Ü4

wooden, wood powders are usually inexpensive, with the exception of special cases. Wood powder is effortless as a starting material available in large quantities. On the other hand, thermoplastic polymers, in particular polyolefin polymers, are also inexpensive and available as starting materials in large quantities, since the price and availability of the starting monomers are cheap and as the polymerization technology is making great strides.

In view of these ratios, it seems appropriate, an inexpensive moldable preparation by combining a To win wood powder and a thermoplastic polymer, in particular a polyolefin polymer together. This method however, does not lead to the desired result. It is based on the fact that when a preparation is heated and molded made of a thermoplastic polymer such as a polyolefin polymer and a wood powder, the molding usually has poor compatibility between the polymer and the wood powder, so that the mechanical strength of the molding is low and also the hardness thereof is poor.

The object of the invention is to eliminate these difficulties when using a thermoplastic polymer, in particular a polyolefin polymer, and a wood powder appear. This object is achieved according to the invention by a mixed substance preparation, which is essentially a first thermoplastic polymer, a second thermoplastic polymer and a particulate, cellulosic, high polymer Comprises component which is impregnated with a third thermoplastic polymer and in which the second thermoplastic polymer at least partially forms a graft polymer with the first thermoplastic polymer.

With the preparation according to the invention, molded parts can be produced with a wood powder content that is not itself «? has load-bearing or dimensionally stable properties = one has | thus a new type of molding material is available. The invention er j enables a particularly advantageous production of form! substances of the type described.

. 3uyb4ö / 11zö ————

19TTiO?

In a further development, the invention proposes a method according to which a mixture of a cellulosic, high polymer Particulate component, composed of a thermoplastic polymer in particulate form and a vinyl monomer into a polymerizable one State and the polymerization is carried out in such a way that essentially no polymerizable, free, continuous phase of the vinyl monomer occurs, so that a polymerization product is essentially inform of loose particles.

Details and possible applications of the invention emerge from the following detailed description, which is based on more general Considerations and on the basis of exemplary embodiments are used to explain the invention.

As already stated, the polymer component comprises the preparation According to the invention, two polymers, one of which is at least partially a graft polymer with the other polymer forms; The filler component is a cellulosic ,. high polymer particulate compound with a thermoplastic Polymer is impregnated.

Because of the investigations is an ideal preparation for the formation in ^r lörmteile a composition has proven to be interesting that one. Polyolefin polymer as the first / thermoplastic polymer. Comprising thermoplastic polymer compatible therewith with a transition temperature of the second order above 4-0 ° C. and a cellulosic, high-polymer component in particulate form. By using the two polymer components in the form of a graft polymer, it is also possible to achieve a noticeable improvement in the physical properties, in particular the strength, of the molded objects.

By using cellulosic, high polymer particles impregnated with a thermoplastic polymer as cellulosic, high-polymer particle components for the purposes of the invention, a noticeable improvement in physical properties is achieved Properties, ^ -in particular the strength and the

909848/1126

"TTTFUT

Heat shrinkage of the molded objects compared to those items that are manufactured using conventional methods. There is also a noticeable improvement the moisture absorption, the dimensional stability and the resistance of the objects.

It has already been pointed out that the first component of the preparation according to the invention is a thermoplastic polymer which is called the first thermoplastic polymer and is a homopolymer or a copolymer of vinyl monomers represents. Viny! Monomers denote polymerizable, unsaturated ones Monomers each with at least one ethylene-like unsaturated bond. An example of this first thermoplastic Polymer is a polyolefin polymer. Examples of such polyolefin polymers are homopolymers and copolymers of Olefins such as ethylene, propylene and butene-1. This polyolefin polymer can also be a copolymer of an olefin and a small proportion of a non-olefinic monomer, e.g. Vinyl acetate, acrylic acid or an ester thereof, methacrylic acid or an ester thereof.

Other examples of this first thermoplastic polymer are Polymers of non-olefinic vinyl monomers, e.g. polyvinyl chloride, polymethacrylate esters (especially lower alkyl methacrylates and preferably methyl methacrylate), polyacrylate ester, Polystyrene, polyvinyltoluene, poly-6-methylstyrene and poly-styrene-acrylonitrile.

The second thermoplastic polymer as the second component of the preparation according to the invention is a polymer with similar thermoplastic behavior as the first polymer and is essentially as determined as the same. However, if a polyolefin polymer is selected for the first thermoplastic polymer, the second thermoplastic polymer is preferably a different polymer. A thermoplastic polymer which is compatible with a polyolefin polymer and has a transition temperature of the second order above 40 ^° C. is particularly preferred, examples of such polymers being binding

909848/1126

Τ9ΤΠΤΡΓ

- kl

said thermoplastic polymers of non-olefin-type Vinyl monomers, particularly preferred examples of such Polymers are polymers of styrene, lower alkyl methacrylate and divinylbenzene.

A feature of the preparation according to the invention is that the second thermoplastic polymer is at least partially a graft polymer with the first thermoplastic polymer This means that a composition can be obtained, ν / ο the vinyl monomer for the second thermoplastic polymer ο ine graft polymerisation compared to the first thermoplastic Enters into polymer that forms the base polymer.

Depending on the graft polymerisation technique, in some cases a polymer of the Viriylmonomere BeLbSb ₅ which benubab Lab for graft polymerisation is obtained as a by-product: Within the preparation according to the invention one can also utilize graft polymers in which such polymers are contained as a by-product ,, Satisfactory results are achieved as long as only the two polymer components form a graft polymer at least in part. The graft polymers can be formed by any conventional technique, for example by pre-irradiation, by simultaneous irradiation and by the air oxidation technique.

The third component of the preparation according to the invention is a composite material, which by impregnation of a cellulose » arfcigen, hochpolymerη substance in particle form with the help of a ■ 1 ritten thermoplastic polymer is prepared, albeit a useful material for use as seLLuloeeiuMilge Component LfJb, you can also use other eelluLoiKmrbige ? i!; offtj, bapsr.- Purified cellulose aoLbab, Sbroh, fibrous material and Gel.Luioso fibers, each depending on the hrfofdemluoon. Daa third thermoplastic polymer for impregnation the öeLLuloaöijboffes can daa equal or an unmihledliohaa be compared to the first two polymers, In addition, this third thermoplastic polymer must be «« Did not necessarily mean «to be in polymer,

909848/1126

IAO ORIQiNAt

whose second order transition pimkb is above 40 G.

However, it is normally preferred that this third polymer with which two is equal to polymer. Hence, are preferred Examples the same as the examples given above for the first and second polymer,

A useful technique for impregnating this thermoplastic polymer is to impregnate the high polymer Cellulosic fabric with vinyl monomer and in the process of polymerization this vinylinomer in the cellulose fiber so that the polymer is formed in situ. In this "case, the polymerisation can be triggered by the same Avis release process that occurs at of the mentioned graft polymerisation «! is,

Depending on the polymerisation conditions, the Possibility that the bluraiopLaotiaciie polymer at least partially i? iii Pfropfpoiyineriaat with the h -: »chpol.jfiasren Gsllulose- = oboff forms, fol ^ li ^ h looks at the thurmoplaüfeLache Poly » Iner-Imprägrileruiig not exclusively on one physical one Mixture, in addition, the presence of a polymer component, which is not impregnated in the Celiulosesboff and which as By-product is added, not harmful »

This cellulosic, high polymer material, 'dsr with; the thermo = - plastic polymer is impregnated, is in 'Ueilehenform. This Tallchensubsröitung can inform from a raw material a higher polymer cellulose toffee can be obtained, which is already in particle form and in which the thermoplastic Polymer is formed in situ, the particle structure being = remains to be paid off,

A particulate substance is understood to mean a physical state οinss granular substance, "that with sufficient Smaller grain size available and then one in the v; uterine represents a freely flowing substance, such a state is realized by substances in the form of a fine powder. In detail Isb it appropriate that the grain size is smaller than 10 mesh sizes lab (measured according to dea liormalsisb according to Tyler),

BATH ORIGINAL

ΤΒΊΊ8ΙΓ5

_ 7 -

If the grain size of this particle component is large, e.g. is between ΊΟ and 30 mesh sizes, one of these shows Preparation of the molded part has a remarkable pattern through the cellulose fabric that is visible from the outside.

The mixing ratios of the three components of the preparation according to the invention can depend on the desired. Properties of the molded parts formed from the preparations are selected. Generally speaking, it has proven to be useful proved that 10 to 150 parts, preferably 20 to 100 parts, of the particulate cellulosic fabric associated with the third thermoplastic polymer is impregnated with 100 parts of a blend of the first and second thermoplastic polymers Conveniently, the weight ratio is of the first and second polymer of the above mixture between 5:95 and 95: 5, in particular between 20:80 and 80:20. The weight ratio of the cellulosic fabric and the polymer impregnating agent is between 98t2 and 2:98, preferably between 80:20 and 20:80.

The mixture of these three ingredients can be carried out by any mixing method with uniform intermixing of the components are generated. For example, the components can be dry in the loose state in the form of the individual parts concerned be mixed, for example in a Nauta mixer; it is also one Melt blending possible by means of a drum or an extruder.

However, the preparation for producing molded parts according to the invention is conveniently carried out by the following method obtained according to the invention.

This method is characterized in that a mixture of a cellulose-like, high polymer component in part ₌ chenform, of a thermoplastic polymer in particulate form and a vinyl monomer added in a polymerizable state and the polymerization is carried out in such a way that essentially no polymerizable free , coherent phase of the vinyl monomer occurs, so that one

909-848 / 1126

Polymerization product obtained essentially in the form of loose particles.

Thus, a feature of the method according to the invention is the use of a particulate substance, for example wood powder, as a cellulosic, high polymer material. In well-known wood-plastic Composites, it has been comparatively difficult for the monomer to penetrate completely into the interior of the wood because the wooden parts used were comparatively massive. If, on the other hand, wood in particle form according to of the invention is used, there is no difficulty in a complete impregnation.

Normally, the monomer is allowed to penetrate into the cellulosic material by degassing the cellulosic material in stages, by bringing the cellulosic fabric into contact with the monomer under reduced pressure and then atmospheric pressure switches on again or applies an overpressure. Through the However, depending on the particle size of the cellulose material, there are cases in which it is sufficient to aas monomer and the cellulosic fabric in connection with one another, too bring. If a solvent is also used during the impregnation process, the same can happen easily removed.

Another feature of the process of the present invention is that the polymerization conditions are established within the mixture of the particulate, high polymer cellulosic fabric, the vinyl monomer and the vinyl polymer in particulate form. As a result, part of the vinyl monomer can form a graft polymer with the co-present vinyl polymer in particulate form. As a result, the high polymer cellulose material, the vinyl polymer initially present and a vinyl polymer formed by the polymerisation of the vinyl monomer are present in intimate mutual mixing within the treated material; these components have excellent mutual compatibility. Therefore molded parts formed from this preparation do not show any defects due to phase

909848/1126

separation due to changes due to aging.

■ Another feature of the invention is that the so prepared Substances in the form of particles can be obtained in a comparatively loose context or completely separated. In detail, these substances appear in a state of essentially free flow, either already completely separated from each other as loose particles or in a form that allows easy separation into loose particles by being the product is easily crushed or banged. With a view to the fact that the invention relates to a mixed substance preparation is, this feature is extremely significant.

As already mentioned above, wood powders are the most common starting materials for the particulate, cellulosic, high polymer component in the application of the invention. In addition, such cellulosic materials as straw fibers in the form of woven fabric or other woven fabrics can be used with good success * The ratio of the cellulose component within the particle mixture to the thermoplastic polymer is between 2 and 98%, preferably between 8 and 70% by weight.

Another starting material is a vinyl polymer, which is used as the first thermoplastic polymer is designated. A polyolefin polymer is preferably used. This polymer becomes particulate, preferably with a grain size below IQ mesh sizes, similar to the cellulose-like, high-polymer material used.

The vinyl monomer as a further important starting material in the process according to the invention is preferably such that it is present under the Polymerisationsbedingimgen ¹ in liquid phase. In view of the object of the invention to obtain a preparation in particulate form, this monomer must be such that it will dissolve the vinyl polymer under the polymerization does not appreciably $ otherwise it would have to be used in a solution, the solvent dissolves the polymer under the Polymerisationebedingungen not appreciably .

909848/1126

—_ - ^ _ _____ _ 1 y 11804

Specific examples of such monomers are styrene, acrylic ester, Methacrylic ester, vinyl acetate, acrylonitrile, divinyibenzene and Vinyl pyridine. These and other monomers can be used alone or as mixtures of two or more components. the Choice of these monomers in pure form or as a mixture to form a thermoplastic polymer with a. Second order transition temperature above 40 ° G is known to those skilled in the art common due to the general polymer chemistry.

In the context of the process according to the invention, a mixture from the above-mentioned important "starting materials" polymerization conditions exposed. The polymerization takes place in such a way that essentially no polymerizable, free ! coherent phase of the vinyl monomer occurs. I.e. that Monomer should not be in a state that is contiguous Phase of the polymer formed from this monomer can form with the formation of the polymerization. Because then instead of an appearance of loose, separated particles, the endotoff would form tough lumps so that a It is not easy to smash or grind.

Therefore, according to the technology according to the invention, the monomer is exposed to the polymerization conditions in a state w.rin most, if not all of the monomer through .sorption is bound, i.e. by absorption or adsorption, to a particulate mixture of the particulate, highly polymeric Cellulose components and the thermoplastic vinyl polymer in particulate form. A suitable procedure is available e.g. in the use of a monomer in an amount of 10 up to 150 parts by weight versus 100 parts by weight of the particulate mixture of the cellulosic component and the thermoplastic Vinyl polymers.

To suppress the formation of polymerizable, free, continuous phase of the monomer can destroy the continuous phase as a result of an excess of monomer by is preferably done carefully in the presence of a diluent stirred. In addition, if "a

909848/1126

SAD ORIGINAL

free, coherent phase of excess monomer the same obtained in an unpolymerized state by regulating the polymerization conditions, for example by pre-irradiation in radiation polymerization.

While the polymerization can be carried out by any technique, a preferred technique is that Exposure to ionizing radiation. In this case, the polymerization can also be carried out using the so-called pre-irradiation process perform, after which the particulate mixture of the cellulosic fabric and the thermoplastic vinyl polymer irradiated with ionizing radiation and then brought into contact with the vinyl monomer.

By using a solvent in carrying out these reactions, the yield of the reaction can be further increased in some cases and highly desirable results can be obtained. Furthermore, the amount of radiation power required can be reduced by introducing a catalyst, for example azo-bis-isobutyronitrile or benzoyl peroxide, into the reaction mixture. The ionizing rays for triggering the polymerization are of a known type, for example / Q, γ and X rays, neutron rays, accelerated electrons or heavy corpuscular rays.

Various changes and modifications to the present invention Procedures are possible. For example, you can add additives such as fillers, dyes or pigments as well as any necessary Add stabilizer; the particulate, high polymer component can also be colored beforehand.

In addition, the preparation according to the invention can be in various Way to be changed and modified. For example, you can use other fillers, dyes, stabilizers, plasticizers and mix other polymers with the components if necessary. In addition, these changes and modifications are for a every essential component of the preparation is possible.

The polyolefin preparation thus obtained can be heated (e.g. between 160 ° G and 190 ° C) and / or by the application of pressure

909848/1126

be molded into different shape parts, each essentially from a single-phase, homogeneous melting body of polymers and a polymer-impregnated, particulate, boohpolymeren cellulosic fabric that is uniform within-] i-3jb the mixed phase is distributed.

liaifiit das V " ^: esen and the usefulness of the invention still clear! In the following, the following exemplary embodiments are discussed, which serve only to explain the invention and not to restrict the inventive concept.

There are measurements of physical properties in the following Examples are as follows:

Hardness: ASTM. D785-51 (L scale)

Flexural Strength: ASTN. D747 (6 ° bend)

heat shrinkage: 190 ° C (compression molding)

Dimensional stability: 20 ⁰ C (for ? A hours in water)

Embodiment 1

<-in graft polymer made of a polypropylene (PP) (specific weight = 0.91, melt index (MI) = M-) and methyl methacrylate (MMA) as well as a composite of wood powder impregnated with methyl methacrylate (spruce, grain size 10 mesh sizes or smaller) with auspolymerisiertem ΜΙΛΑ were dry mixed in a Nauta mixer, in each case in various ratios as shown in Table 1. The obtained mixture was molded for 10 minutes at a temperature of j 19Ö ⁰ C under pressure; the physical properties of the respective molded part were measured.

Wood powder was a polypropylene / methyl methacrylate graft polymer attached; the samples obtained were measured in the same way «

909848/1126

8AD

- 13 Table 1

Composition (percent by weight), 70 Wood powder /
MMA composite
material _ wood
pul
ver Bend
firm
ability 2
kg / cm Formbe
constant
speed
% run.
No. PP / MMA graft
polymer 1 j 80 Wood powder /
MMA ratios 20th 30th 17 400 3.2 I 1 PP: MMA-Ver
ratio 1 ■ S 70 30th - 17 500 0.5 ^: 2 1: 1 : 1 70 90:10 30th - 18 200 0.6 3 1 : 1 »60 98: 2 40 - 22,000 0.6 4th 1 : 1 '70 90:10 30th - 23 800 0.7 5 1 ^{: 25} i ⁵⁵ 90:10 45 - 12 500 0.2 6th 1 2:98 - 23 500 0.8 I ⁷ 1 67:33 3

Execution 3beisx) iel 2

Styrene, acrylonitrile and divinylbenzene were each graft-polymerized, each with a graft ratio of 30 % with respect to a polypropylene (PP) (specific gravity = 0.91, MI = 4). Wood powder (Sugi, Cryptomeria japonica, grain size 10 mesh sizes or smaller) mixed in a Nauta mixer. The mixtures obtained were molded under pressure to give a test specimen which was subjected to the tests given in Table 2.

Separate samples of the wood powder were then impregnated with each of the above vinyl monomers, which were then up to were polymerized into a degree of 10 percent, so that a wood powder composite was obtained. These substances were then using the graft polymers of the polypropylene / vinyl monomer of the above composition are mixed to thereby give specimens obtain.

In addition, test specimens made of polypropylene alone and a combination of a simple mixture of polypropylene, a polymer of a vinyl monomer and the wood powder

909848/1126

- 14th of attempts • • Ι I. Fh I. O I. Ph at these specimens are in d LfN D- - - IfN • specified. ο ¹ H. • Η I Φ ο CIPh • Η O rcN O shaped and Fh γ- Φ N > LfN Φ • Η Fh Fh = O O O I. P. I Xi rH rH C ¹ ^ ί> Fh Φ a ι 3 O O O φ CQ U ο O 3 3 · Η O : ο d ■ Ρ LfN ITs O D- O cq co t-t W CQ ω pi Pi Χ> ■ Ρ ^ I. φ KN 3 Φ Ö I _ρ CM CO Ο O : cö Fh O : cö hC ι • Η
Φ ^ ^ ω <! v- O O CM subjected to the same experimental measurements. k • Η co ¹ O Fh O O KN CM The measurement results Fh I ^ OJ I Φ O O O Table 2 pt ι -O Φ N ί> LA O O ^ j- t k O -P O rH rH ζ— O ώ cö CM co Φ-H O 3 O bO-P Φ bC Ij ρ, ^ ~ LfN Φ CO co I. CM CM • Η Φ P. pi ω ff) <H φ O O O φ co I Fh D- τ- KN KN d 1 (Ή Γγν CO OO Fh φ I ₁ Pl ₁ : cö
W. 1 Ph ο co Ph KN 3 Ph KN CsI KN O KN ο O KN KN Fh φ O El I «Μ KN O I Tj Vl O F-ido O O O φ 3 P O D- > Xl CQ O C \ J Fh ^ ^- I. O O φ D- rH rH H Fh O
NS - I O Φ O O • rl SM Φ ft a O U 0) η KN * ~ 4-3 »Η r *> CD KN «I. O r-l EH Γ ~ { d ί i
-H Cj f ^ s O rH J.) ω Fh r. P. JO •H H
O • Η rH •H CQ rH j3 rH its VD f. -H CT ^ O ιΗ rH H
O • Η O O CQ %? U Φ ω • Ρ v> co -P CQ m N • Ρ ffN 3 Φ ■ °

909848/1126

50 g of a graft polymer (weight ratio of the composition PE: MMA = 2: 1) of a polyethylene (PE) high density (specific weight = 0.965, ULI. = 4.5) and of methyl methacrylate (MMA) and 50 g of wood powder PMMA -Composite (weight ratio of the composition wood powder: PMMA = 2: 1), obtained by impregnating a wood powder (spruce with a grain size of 10 mm or less) with methyl methacrylate and by purifying the! «Ethyl methacrylate, were mixed dry in an I: - <uta mixer. The mixture obtained was molded under pressure for 10 minutes at 190 ° C. The molded parts were examined and showed excellent dimensional stability when they had absorbed water, high gloss and high flexural strength.

Samples of polyethylene alone and a graft polymer of polyethylene and methyl methacrylate (weight ratio of the composition PE: MMA - 1: 1) were prepared accordingly.

The measurement results of all test pieces are shown in Table 3.

Table 5

running Composition (weight percent) ruff 100 Wood powder /
PMMA composite
material 50 hardness No. PE / MMA Pf
polymer 50 Wood powder;
MMA PErHMA PE alone (100) 21 1 1: 1 42 CVJ 2: 1 2: 1 68 3

Ba e fixed ext

kg / cm "

8 500

10,000 15,300

VV poor

shrink

fung

2.1

1.5 0.5

external ersehe aiming S image

same as PE 4-

A venturi n

Embodiment 4 50 g of a Pfr-or.fpoljTEers made of a polyethylene (PE) lower

909848/1126

ORfSINAL

ΊΓΓΤοΤΓΖΓ

Density (specific gravity = 0.918, M.I. = 4) and methyl methacrylate (MMA, weight ratio of the composition PE: MMA = 2: 1) and 50 g of a wood powder / PMMA composite, which by Impregnation of methyl methacrylate into a wood powder (spruce, 10 mesh sizes or less) and obtained by polymerizing was (composition weight ratio MMA = 2: 1) were dry blended in a Nauta mixer; the received Mixture was pressure molded at 190 ° C for 10 minutes. The molding was then examined and it was found excellent dimensional stability after absorption of water high gloss and high flexural strength.

Correspondingly, samples of polyethylene alone and one were then made Graft polymer of polyethylene and methyl methacrylate (weight ratio the composition PE: MMA = 1: 1) finished.

The measurement results on these samples are given in Table 4.

Table H-

Composition (weight percent)

PE / MMA graft polymer

Wood powder /

PMMA coating

composite

hardness

Flexural strength
speed ρ
kg / cm

V / poor

shrink

fung

exterior
Appearance

PE alone

(100)

1: 1

2: 1

100

50

2: 1

50

not measurable

20th

37

3,000
5,000

9,000

2.0

1.1

0.7

as well as PE

Aven turin

909848/1 t26

Embodiment 5

Approximately equal amounts of powder with 30 mesh sizes or less of Spruce, sugi (Cryptomeria japonica) and birch were mixed; into the mixture was a polypropylene powder with M.I. = 4-, 2y specific weight = 0.91, particle size 30 mesh sizes and less, entered in different amounts, so that different mixtures were obtained. Any of these mixes was carefully degassed in a corresponding real-life barrel and then added a certain amount of a solution of methanol and vinyl monomer in the ratio 1: 4 to this mixture. the various mixtures were mixed for 10 to 60 minutes for impregnation to occur; on it was every mixture with 5 megarads at room temperature by a linear accelerator irradiated to obtain polymerization.

For each wood powder or polypropylene alone and the vinyl monomer solution Similar samples were prepared.

The weight increase ratio and the conversion number according to the following definition has been prepared for the various and dried samples.

The results are given in Table 5 and show that normally when polypropylene is present in the wood powder, the conversion number is higher than when the wood powder is used alone.

Gewi ent increase ratio

Reaction product - (A)

(Weight (A) of the wood powder + vinyl polymer)

χ 100

Conversion number

converted monomer impregnated monomer

χ 100

90-9848 / 1126

- 18th - ) - Poly 5 5 Vinyl monomer Trains Weight- J! I 804 Table I. Mixture composition (weight percentage) - propy 40 40 sat increase— 60 len - - Art lot behaved- Raw material 55 40 ni H Conversion 20th 40 AX-I-W lung Wood powder 60 - Methy1- number - metha- 20th running 55 1 40 crylate 40 19.3 % No. 60 20th 5 - Il 40 60 20th It 40 1 40 40 Il 40 - 28.9 80 20th 55 M. 40 27.8 59 60 59 Il 40 35.0 2 55 60 Il 40 62.5 - - 3 40 20th 80 Il 20th 66.7 41.7 4th 20th 60 - Il 40 65.8 52.5 5 5 H 40 65.8 93.6 6th 1 20th Styrene 40 66.2 100 7th It 25, o 98.5 8th Il 40 5.3 98.5 9 Methyl- 40 9.6 99 ' 10 acrylate 40 15.4 100 11th It 40 8.0 . 12th It 19.0 14.4 13th Divinyl 40 33.4 23.1 14th benzene 40 64.8 Il 5.0 28.7 15th vinyl 40 50.0 16 acetate 40 9.6 97.0 17th M. 15.3 7.5 vinyl 40 18th pyridine, 45.2 14.3 19th η 13.2 23.0 20th 33.4 68.0 21 21, i 22nd 50.1

909848/1126

1911804
- 19 -
Embodiment 6
Polyethylene powder (MI «4, specific gravity = 0.918, grain
size 20 mesh sizes and less) was in weight ratio
1: 1 with spruce wood powder (grain size 30 mesh sizes and wh
niger) mixed; the mixture obtained was poured into a corresponding
corresponding reaction vessel set. A solution inform a
Mixture of methanol and methyl methacrylate in a weight ratio
nis 1: 3 in an amount of 40 percent by weight based on
Methyl methacrylate is added to the mixture in the reaction vessel
adds. The entire mixture was mixed with it for 30 minutes
an impregnation was obtained. Then there was an irradiation
from 1 megarad of cobalt 60-Jf rays at room temperature. That
Product was then dried and the weight gain ratio
and the conversion rate were determined.
Similar samples of holu powder and polyethylene alone without the
other ingredients have been prepared, and the appropriate
Values were measured.
The measurement results are shown in Table 6.
Table 6 Mishun gskomp . (Percent by weight) Weight
increase-
relationship
% Conversion
lung
number
% running
No. wood
powder Poly
ethylene methyl
methacrylate 21.4
57.0
57.3 32
85.6
86 23
24
25th 60
30th 30th
60 40
40
40

9 0-9-8 4 8- / 1126

Embodiment 7

Sugiwood powder (Cryptomeria japonica), grain size 20 mesh sizes and less, with an equal part by weight of one Polyolefin polymer powder (grain size 20 mesh sizes and less) mixed. The mixture obtained was in a vacuum of 2 mm Hg degassed in an appropriate reaction vessel. A solution of a mixture of methanol and methyl methacrylate in a ratio of 1: 5 was added to the degassed mixture in an amount of 40 percent by weight based on the methyl methacrylate joined. After a mixing time of 60 minutes to achieve impregnation, the mixture was exposed to 3 megarads with the electron beam of a linear accelerator. The reaction product was dried. Then the weight increase ratio became and the conversion number is determined. A corresponding A sample of the wood powder alone with no polymer was also used prepared.

The measurement results from these samples are shown in Table 7 below.

Table 7

running

Mixture composition (weight percentage)

Wood powder

thermoplastic; Vinyl monomer
Art

added

lot

methyl meth ~
acrylate

Certainly

to

mated

Umwanä luigs number

60
30th

30th

30th
30th

Polypropylene

Ethylene * 2)

Propylene

Copolymer

Polysty- * 3)
rol

Polyvinyl - * ^ -)
chloride

30 30

30th

30th

40
40

40

40
40

14th
54.2

54.7

48.7
52.3

21.0 81.2

82.0

73.0 78.5

909848/1 126

ORIGINAL

Note:

• 1) • 2)

• 3) * 4)

M.I. = 4.2, specific gravity = 0.91

M.I. = 1 specific weight »0.905 propylene content = 90 percent by weight

M.I. »7 specific weight = 1.05 M.I. according to ASTM, D-1238

specific weight = 1.4

Embodiment 8

Spruce wood powder (grain size 20 mesh sizes and less) was made with the same weight of polypropylene powder (grain size 20 mesh sizes and less, M.I. = 4.2, specific weight » 0.91), the mixture was poured into a corresponding reaction vessel set. One part by weight of methanol was mixed with 5 parts of methyl methacrylate; to the solution obtained i was azobisisobutylnitrile in an amount of 1% based on of the methyl methacrylate added. Then 40 percent by weight of the methyl methacrylate contained in the solution Wood powder-polypropylene mixture added. The entire mixture was mixed for 60 minutes to achieve impregnation. The electron beam of a linear accelerator was then irradiated at 1.5 megarads. The reaction product was dried. Then the weight increase ratio and the conversion number were determined and found to be 54.7% and 82% obtain.

A corresponding sample using wood powder alone was prepared and measured; the weight gain ratio in this case resulted in 14.3% and the conversion figure to 22%.

Embodiment 9

. Spruce wood powder (grain size 20 mesh sizes and less) was made with an equal part by weight of polypropylene powder (grain size 20 mesh sizes and less, M.I. "" »4» 2, specific Weight x 0.91) mixed, the obtained mixture was subjected to electron irradiation of 2 megarads from a linear accelerator outgassed. Then the irradiated mixture became

909848/1126 ■ ""

placed in a reaction vessel and degassed. Then became a 20 percent methanol solution of methyl methacrylate in one Amount of 60 percent by weight of the methyl methacrylate added. A reaction took place in the substance obtained at 70 ° G for 60 minutes long off. The reaction product was dried, the weight increase ratio was determined and measured to be 31%.

Correspondingly, the weight increase ratio was determined for a similar sample from a wood powder without polypropylene and measured as ψ / ο.

Embodiment 10

A number of samples of preparations for molding which nact Examples 5, 6 and 7 were obtained under pressure at a temperature of 190 ° C. for 10 minutes Test specimens formed, which were then examined for certain physical properties. The measured values are given in Table S. specified. ". ■" -,

The measurements were obtained according to the following measurement rules:

Flexural Strength: ASTM, D74-7 _- ': j Hardness: ASTM, D785-51

Heat shrinkage: 190 ° C (compression molding) Water absorption: 20 ° C, 24 hours ..

₅ , .. 90 9848/1126

running
No. Table 8 more thermoplastic ' Material Vinyl monomer • Trains
sat
lot Bending
firm. ^
speed
ρ hardness Warmth-
shrink
fung water
absorp
tion
Weight ^ O
C. Mixture compositionC weight percent.) Art Trains
sat
lot Art kg / cm cm / cm - Wood
powder - 10 500 R-67 0.15 0.001 27 Polypropylene : 100 - 40 23 200 L- 80 0.003 0.12 dd 30th Methyl- 30th methg- co 13th crylate 40 19,000 L- 75 0.003 0.12 O 20th dd 40 Styrene 40 11,000 0.003 0.11 ' co _ 20th Il 40 Vinyl-
acetate - 35,000 M- 70 0.005 0.001 ι OO 29 20th Polystyrene 100 40 41,000 M- 80 0.0001 0.12 OO _ ti 30th Methyl- N> 30th Metha- cn - crylate - 47,000 R-100 0.003 0.001 30th Polyvinyl chloride 100 - 40 62,000 L-110 0.0001 0.12 - Il 30th Methyl- 30th metha- - crylate - - - - more Hardwood panel 100 - than 30 -
ft ... _ - - - ■ more _ Wood (Sugi) 100 _ than 30

ι y 11 ö υ λ

Note: polypropylene:

Polystyrene:

Polyvinyl chloride;

Hardwood board:

Sugi (cryptomeria japonica) M.I. ■ 4.2, specific weight

= 0.91

M.I. “O.54, specific gravity

= 1.05 P = 1.100, specific gravity

Moisture content 8% specific weight * 0.9? oil treated

Moisture content 13% specific weight

0.3

909848/1126

Claims (12)

) / 1., mixed material preparation for molding in molded parts, marked Characterized by essentially the following components: a first thermoplastic polymer, a second thermoplastic polymer and a particulate, cellulosic, high polymer component that is impregnated with a third thermoplastic polymer, the second polymer with the first polymer at least partially a graft polymer forms. 2. Mixed substance preparation according to claim 1, characterized in that that the cellulosic component is in the form of wood particles. 3. mixed substance preparation according to claim 1 or 2, characterized in that that the second polymer is the same as the third polymer. 4. Mixed substance preparation according to one of claims 1 to 3, characterized by a first polymer in the form of a polyolefin polymer. _O 5. mixed substance preparation according to claim 4, characterized by a polyolefin polymer from the group of polyethylenes, crystalline Polypropylene and Polyethylene-Propylene. i 6. Mixture preparation according to one of claims 1 to 5j da- ' characterized in that the second polymer is compatible with the first polymer and a transition temperature second Order above 40 ° 0. 7. mixed substance preparation according to one of claims Λ to 6, characterized by a second polymer from the group of polymers of lower alkyl methacrylates and polystyrenes. 909848/1126 8th.
Process for the production of a mixed material preparation for shaping into molded parts, characterized in that a mixture of a cellulose-like, high-polymer component in particle form, of a thermoplastic polymer in particle form and a vinyl monomer is put into a polymerizable state and the polymerization is carried out in such a way it is stated that essentially no polymerizable, free, coherent phase of the vinyl monomer occurs, so that a polymerization product is obtained in essentially loose particles. 9. The method according to claim 8, characterized in that in the polymerizable state at least a majority of the vinyl monomer in a sorbent state with respect to the particle mixture the cellulosic, high polymer component and the thermoplastic polymer is present. 10. The method according to claim 8 or 9 »characterized in that that in order to produce the polymerizable state, irradiation with ionizing rays takes place. 11. The method according to any one of claims 8 to 10, characterized in that that the cellulosic, high polymer component is added in particulate form as wood particles. 12. Process according to one of claims 8 to 11, characterized by a thermoplastic polymer from the group of polyethylene, the crystalline polypropylenes and the poly-ethylene-propylenes. 13 · The method of any of claims 8 to 12, characterized in that the vinyl monomer is at least one monomer selected from the group of lower alkyl methacrylates and Sryrole entv.It. I ⁴ T. The method according to any one of claims 8 to 13, characterized in that the vinyl monomer inform a? alcoholic 909848/1126 Solution is present and that the state that is susceptible to polymerization is through Irradiation with ionizing rays is generated. 9 0 98 4 8/1126 originally inspected