DE1494125A1 - Polymeric compositions of matter - Google Patents

Description

The filing priorities of June 27, 1960 and June 9, 1961 are claimed.

The present invention relates to novel polymeric compositions of matter and, more particularly, to novel vinyl chloride polymers containing compositions of matter

High molecular weight polyvinyl chlorides tend to do so to become brittle and since this tendency limits the usefulness of the polymers, various attempts have been made under " taken to eliminate the inadequacy. Plastic adorned Polyvinyl chlorides have been known for years and are generally considerably less brittle than the unmodified ones Polymers; but the addition of plasticizers, which are generally liquid, leads to an undesirable reduction in the

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Softening point of the product. Examples of the proposed Plasticizers are the phthalates and adipates and also various low molecular weight polymers and mixed polymers, such as they are described in British Patent Specification 703,252.

The copolymerization of vinyl chloride can also Reduce the brittleness of the product, but it generally causes other undesirable physical properties in the product.

Mixtures of polyvinyl chloride with butadiene copolymers, such as one has a mixed polymer of butadiene and methyl methacrylate * recently proposed because they usually have good impact resistance and their aging properties are poor. Various attempts have been made to obtain a material which has the desired properties of these mixtures, but without their aging properties.

Mixtures of polymethyl methacrylate and polyvinyl chloride are essentially compatible; yet they show poor impact resistance, and while using blends of polyvinyl chloride Polyethylenes show a certain increase in impact resistance, they are notch sensitive.

It has now been found that mixtures of polymers of vinyl chloride with certain copolymers, of which at least one monomeric component ethylene 1st, good impact resistance and very good aging properties as well as good tensile strength and show flow properties.

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U94125

According to the present invention, novel polymeric substance are vorgesehlagen · compositions consisting of 98-60 Oei ».- Ji of a polyvinyl chloride and from 2 to 40 Qew.-jG · a solid product that old by co-polymerizing Xthylen

What is obtained is a monoethylene-like unsaturated compound ^ van der

at least one of the free valencies through a monovalent radical of the formula - CN or - COOR · in which R is hydrogen

or a monovalent hydrocarbon radical is or by the divalent radical of the formula - CO- 0 - OC- is removed from at least two of the remaining valences Hydrogen atoms are bonded to give a polymerization product, which 7 to 95 Gew.-jC units of the mentioned contains aonoäthylenartlgen unsaturated compound

Polyvinyl chloride is intended to mean homopolymers or mixed polymers of vinyl chloride with up to 20% of another polymerizable Monomers are understood.

Compositions of materials which contain less than 2% of the polymerization product show no appreciable decrease in the particle size compared to polyvinyl chloride alone, while compositions of materials containing more than 40% of the product mentioned tend to have an undesirably low tensile strength. Mixtures of 5 to 15% are preferred % By weight of the polymerization product, as these generally have good impact strength combined with good flow properties and are particularly useful for pressing applications «

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In general, look shown "that" if daa polymer! sat lonaprodukt contains less than 7 weight jtf the monoäthylenartigen unsaturated compound Zerreissfestiglceit of the mixture is affected in the opposite Riohtung. On the other hand, mixtures of the vinyl polymer with a polymer product containing more than 95% of the compound mentioned show insufficient change in brittleness compared to unmodified polyvinyl chloride. It has been found that "normally the best results in terms of impact strength and tensile strength are achieved" when the said polymer solution contains 15 to 75% by weight of the monoethylene type unsaturated compound.

Examples of the compounds «those with ethylene to form the polymerization products used in the present invention Can be polymerized "are methyl acrylate, ethyl acrylate, Butyl acrylate «isoamyl acrylate» 2-xthylhexyl acrylate, Methyl methacrylate, acrylonitrile, acrylic acid, dimethyl maleate, Diethyl maleate «dimethyl fumarate» diethyl fumarate «maleic acid, Maleic anhydride «fumaric acid, methyl α-chloroacrylate and the like. Preferably the monoethylene type unsaturated compound should be used are selected from the class consisting of acrylic and methacrylic acids, their esters and nitriles and maleic and Fumaric acids and their esters exist because of their ready availability. Of these, methyl methacrylate and ethyl acrylate are popular because of their ready availability and reasonable cost preferred.

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BATH ORIGINAL

If necessary, a third component can be added to the polymer! sation product can be incorporated and another Ethylene-like unsaturated hydrocarbon «such as propylene, isobutene or butene-1 or can be a Be nononeres, which is selected from the group 1st »die consists of monoäthylenartlgen unsaturated compounds old at least one polar group. Examples of such Compounds are acrylic acid · its esters and nitriles »methacrylic acid, its ester and nitrile, shark acid, its ester and Anhydride, fumaric acid and their esters and the vinyl esters such as vinyl acetate and vinyl propionate.

The polymerization can be carried out by any of the well-known processes for the miso-polymerizing of ethylene. she can be done with the monomers in bulk, in solution or In suspension, and manufacture can be batch, continuous, or semi-continuous. For example, the polymerization can be carried out batchwise in a steel bomb take place under high pressure or continuously in a tubular reaction vessel or stirred autoclave. Given- * if so, polymer modifiers, such as chain transfer agents, can be present.

Preferably, the polymerization is continuous in one Carried out stirred autoclave, since better products are obtained with this method.

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The polymeric material obtained by this process can be mixed with polyvinyl chloride in every known catfish « including, for example, mixing in a Banbury mill or on a two-roller mill. Antioxidants, filler4 Lubricants, pigments and any of the other common additives, such as other polymeric substances be added at this stage. Preferably, the mixing method is used with those normally used for polyvinyl chloride Temperatures are carried out; Temperatures from I6O to l80 ° C are generally used * but these are tempera * information by no means fixed limits, but is a matter of " borrowed deviation possible.

In the preferred method, the polyvinyl chloride is first brought into the oil form and then the mixed polymer . mixed with it, since mixtures with good impact strengths are obtained on these catfish.

The end products are usually smooth and shiny »have good impact resistance with a low tendency to brittle and a high breaking energy and very good aging properties shown. They can be subjected to all normal working methods, such as compression forming and calendering, and can be used for films, Foils, press molds and the like. Be used.

The compositions of matter of the present invention show in addition to the above useful properties, also useful flow properties which are useful for pressing applications have considerable importance.

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H94125

The invention is illustrated by the following examples, without limiting them to that. All parts are by weight.

Example 1 ... ..

5 parts of methyl methacrylate, 120 parts of ethylene, and 0.025 parts of di-tertiary butyl peroxide were placed in a steel bomb which was placed under pressure of 1000 kg / cm and er * hitzt to 15O ⁰ C. The constituents were stirred mechanically during the reaction, and pressure was again generated in the bomb with ethylene after each pressure drop of 20 kg / cm ² as the reaction proceeded. When the pressure was released, the yield of polymeric material was 18.2 parts.

The methyl methacrylate content was calculated by Hessen der Amounts of the two monomeric units in the product by infrared spectroscopy using the C-H combination absorption lines at about 2.3 µ; the method used was one Ratio method based on the absorption for the -OCH, -Oruppe of the methyl methacrylate units and the saturated -CSU group of polyethylene. The method was using synthetic blends of the two homopolymers in the form of layered panels calibrated to different amounts of the two in the infrared salary resulted from

both in the infrared ray / to deliver. The methyl methacrylate w

909806/0957 ORIGINAL BATHROOM

The crystallinity of the product was determined by the X-ray Diffraction methods determined.

The Sohmelzflussindex was "measured naoh British Standard 2782 Method 105c at 190 ⁰ C and 2 kg, 6.2. The refractive index was 1.496 »measured at 20 ⁰ C using the Natrlum-D-Linle» The melting point of the crystals was 108 ° C, measured using a heated step polarizing microscope ··

The OemisQh from the mixed polymer and the polyvinyl chloride was produced on a two-roll mill at 160 ° C. The polyvinyl chloride was first treated with a stabilizer. (Mellite IJl, presumably an organotin compound) mixed and then the ethylene / methyl methacrylate polymerization product added and mixed. The melt viscosity of Oemlsches was determined at a shear force calculated vpn 6 χ 10 dynes / cm using a Extensionsplastometers at l8o ° C, such as of 'Clegg in "Rheology of Elastomers", Pergamon Pres * I958 is described.

In these and the following six examples, plates were pressed from the mixture and samples were taken from them in the Festlgkeitsteste used customary shape ("dog-bone") cut. The projections of the samples were treated so that they gave a parallel nominal measuring length of 6.35 πκπ.

Tensile tests were performed using these Samples are taken while stretching at a rate of 18 inches per minute at 20 ° Q and your tension result

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(yield stress) was measured by this method. The same molded samples were also used for a tensile impact test at 20 ^° C., with a weight being dropped from a height of 254 cm onto one end of the sample * while the other was held in a screw clamp so that your The longitudinal axis is vertical. Oils; the energy required to break the specimens was calculated and each specimen was checked for appearance, "In which way the break had occurred," whether a jagged break "indicated by Pall movement at low expansion and shell-like break or a break with high energy expenditure. The number of falls for a jagged fracture was expressed as a percentage of the

'·' ■■■ en

Total number of falls' indicated. The results are

contained in the table below. ^:

% Ethylene / methyl methacrylate in mixture 0

Strength test: tension or elongation 7 ^ 5 562 (tensile test) results (kg / cm ² )

(Yield stress)

Impact resistance number of jagged 100 0 test: fractions (£)

(Tensile Impact test)

Breaking energy 55 I63

(ft.lb/cu.in.)

Melt viscosity (Polsen) 1 χ ΙΟ ⁶ 7.2

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Example 2

The procedure of Example 1 was repeated using 10 TeilenMethylmethacrylat, 117.5 parts of ethylene and 0.05 parts ditertiary butyl peroxide. Implementation was

carried out at 150 ⁰ C under a pressure of 1000 kg / cm ² and gave 20 parts of a product with a methyl methacrylate content of Kyf> and the following physical properties t

Melt flow index (2 kg, 190 ⁰ C) 15 refractive index 1.489

Crystallinity between 0 and

Measured melting point 94 ° C

It was mixed with polyvinyl chloride as in Example 1 below Formation of compositions of matter with the following properties »

% Ethylene / methyl methacrylate in the Oeraisch 0 5 10

Stress test s tension or stretch 745 685.5 5 * 6

result (kg / cm ² )

Impact resistance x% jagged fractions 100 17 0 Breaking energy 55 202

(ft.lb./cu.in.)

SchmeUviskositMt (Poisen) IxIO ⁶ 1,7XlO ⁵ 2x10 *

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Example 3

The procedure of Example 1 was repeated using of 10 parts of methyl methacrylate, 105 parts of ethylene and 0 * 075 parts of tertiary butyl peroxide. The implementation was at 150 ° C under a pressure of 1000 kg / cm and gave 67.7 parts of a product with a methyl methaerarlate content of 60Ji and the following physical property ent

Setneltflusslndex (2 kg, 19O ⁰ C) 17 refraction index 1.497

Krlatalllnltat 15Si Melting point 106 ⁰ C

It was shot with polyvinyl chloride as in the example. 1 mixed and 'gave fabric compositions with the following properties 1

% Ethylene / methyl methacrylate 0 5 10 20

in the Qemish

Obligation s
te *%
t 3voltage *> or 8ti- «ck-.
result (kg / cm ² ) 743 724 626 509.5 »Ohlagfeetlg-
»« It test: Jf baggy breaks 100 17th 14th 0 Breaking energy
(ft.lb./cu.in.) 55 293 263 858

(Polsen) IxIO ⁶ 2.2xlO ⁵ 6.4x10 * 2.6x10 *

coherence

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Example 4

Exactly the same amounts of monomer and catalyst as in Example 3 were mixed in a corresponding process under the same pressure "and temperature conditions, however, used with a yield of 46 parts · The product had a methyl methacrylate content of 75 £ and the following physical properties t .

Sea flow index (2 kg, 190 ⁰ C) Refractive Index XrIstallinltat Melting point

26th

between 0 and 94 ° C

Bs was mixed with polyvinyl chloride as in Example 1 and gave compositions of matter with the following properties *

% Ethylene / methyl methacrylate in a mixture

10

Strength test: tension or stretch 745

result (kg / cm)

Impact resistant

keltsteet: % jagged fractions 100

Breaking energy 55

(ft.lb./cu.in.)

SohmeltviskosltKt (Polsen) 1x10 *

699.5

145

, 2x10 *

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⁵ y,

RK3INAI

U94125

Example 5

The procedure of Example 1 was repeated using 40 parts of methyl methacrylate, 118 parts of ethylene and 0.025 part of benzoyl peroxide. The reaction was kg at 100 ⁰ C under a Bruek of 1200 / ^cm2 performed and were 27 parts of a product having a methyl methacrylate of 90Jf and the following physical properties "

Melt flow index (2 kg, 19O ⁰ C) Refractive index Crystallinity

0.06 1.490 nearly 0

It was mixed with polyvinyl chloride as in Example 1 and gave compositions of matter with the following properties * stocks:

% Ethylene / methyl methaorylate in a mixture 0 5

Strength test t Tension «or _p stretch
Result (kg / cnr) 745 710 685.5 Impact resistant
ability test I. % jagged fractions 100 75 Breaking energy
(ft.lb, / cu, ln.) 55 175 157

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Example 6

15 parts Methylmethaorylat and 94 parts of ethylene was dissolved in 45 parts of benzene and then in the presence of 0.025 parts dltertlXrem butyl peroxide in a steel bomb at 150 ⁰ C and a pressure of 1200 kg / cm polymerized · The product was in separating from the benzene and drying 24 parts with a methyl methacrylate content of K}% and the following

physical properties:

Melt flow index (2kg, 19O ⁰ C) 0.34 Refractive index I.499 Crystallinity 28 * Melting point 110 ⁰ C

It was boiled with polyvinyl chloride as in Example 1 and gave compositions of matter with the following properties:

Ethylene / methyl methacrylate in a mixture

Ability test I. Tension or _p stretch
result (kg / cm) 745 541 Impact resistant "
kei didst S. % jagged fractions 100 0 Breaking energy
(ft.lb./eu.in.) 55 160

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U94125

Example 7

The procedure of Example 6 was repeated using 37 parts of ethyl acrylate, 94 parts of ethylene and 0.025 part of tertiary butyl peroxide in 26 parts of benzene. The reaction was determined at 15O ⁰ C under a pressure of 1200 kg / cm carried out and were 38 parts of a product with a "ethyl acrylate content of 75 ^» by the infrared method · dish as la Example 1 with synthetic mixtures of poly (Ethylaory3b) and polyethylene . The product had the following physical properties

Melt flow index (2 kg, Crystallinity Refractive index

0.26 approximately 0 1,471

Ss was mixed with polyvinyl chloride as in Example 1 and gave compositions of matter with the following proper-. esteemed; ....,.

% Xthylene / Xthylaorylate in Oemisoh. 0

Strength test t Tension ^v or "3 stretching
result (kg / om) 745 * 88 _t $ Impact resistant
keitateet. t % taoky rolls 100 0 • Breaking energy
(ft.lb./ou.ln.) 55 165

When using 2-ethylhexyl aorylate or methyl aorylate instead of xethyl acrylate, similar results are obtained «

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U94125

Examples 8-15

In the following examples, methyl methacrylate, acrylonitrile and diethyl maleate were each polymerized with ethylene and the products bit mixed polyvinyl chloride.

In Examples 8, 9 and 10, the Mischaonoaeren in a continuous reaction vessel polymerized «which was equipped with stirrer devices. The catalyst was 3 »5,5-Trimethylhexanoylperojqrd, the temperature 180 ° C, and the Pressures ranged from 1 * 00 to 1700 at. In Examples 11 up to 15 the catalyst was di-tertiary butyl peroxide and the reaction temperature was about 140 ° C. The polymerization was at Example 11 carried out at a pressure of 2000 at and for the rest at 1200 at.

The physical properties of the oven were tested and the results are compiled in the following tables

The tensile impact test for testing brittleness was the same as that used in Examples 1 to 7 and the impact strength (impact strenth) was further tested using a Bounsfield notch impact test.

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ο to on> *

κ · ■ » not
nocUti-
xed
P.V.C. Examples 8th 9 10 11 12th 13th 15D.1 S. ! ■
! MIA MIA MMt AT THE DAU dXm 79.0 ξ iKttqrXywrtachpolyewa Λ) Miacbaonomerea
it '' 9.6 33 21 3P 18th 18th a65i i i '' '
! <B) Ji voa A) Ui copolymers
>' · O 10 KO * ° . · '5 5 10 ι ■ ■■. · ■ ''
C) % mixed polymer in the mixture 80-100 0 0 0 10 ι-
10 '; ο
I. Oeaisch Phrsilcalleche BiKensohaften
; falling weight % jagged 0.02 fcO7 o. * r 0.12 0.22 Siounsfield curb position (ft.lb.)
j ·· ■■ · .-. · .. ·· 273 1 * 7 70.7 69.3 251.6 176.7 Pliessdpucif (kg / ca ² ) (a) 80 au 4 55 · 5 63.5 77.5 80.2 IAO Vloat softening point ⁰ C (b) 0.91 0A96 0.82 ( 0.735 strength «teat, (e) A) tension or stretching
argebnia kg / cai2 χ 10-5 130 146 - 37 132 110 B) Breohanergie ft.!, Be / cu.in.

MUt - MettaylmethacTyXat; AN - aorylonitrile DXN - DiKthylaaleate

U94125

(a) The pressure was measured in a Macklow Smlth . Plastometer, which is used to squeeze out the polymer Material at 150 ⁰ C required pressure measures at a constant punch speed of 21.9 mm / minute with a punch diameter of 1 * 5875 mm and gives a hatred for the ease of pressing the mixtures

(b) The 1/10 Vicat softening point was measured under Ver; application of a 1.507 mm plate.

(c) The strength tests were carried out on samples in the form of rods, which ^{were stretched at 20 °} C. at 45.72 cm / minute. The samples were 44.45 mm long and 12.7 mm thick and had two semicircular holes with a radius of 4.76 mm cut opposite one another, leaving a neck of 3.175 mm on the long sides.

When using diethyl fumarate instead of diethyl maleate in Examples 12-15, similar results are obtained.

Example 16

A mixture containing $ 90 polyvinyl chloride and 10 pounds of the product which was obtained by polymerizing ethylene together with methyl methacrylate was subjected to a longer weather test over a period of 10 1/2 months. That Polymerization product contained 3J8 # methyl methacrylate.

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BAO ORIGINAL The results of the tests are summarized below Aging tent in months

1 5

6 Io

Fixed result eaten at 45 _A 72 mm / minute at 20 ⁰ C (kg / cm ² χ 10-3)

0.6

0.6? 0.588 0.6

jagged breaks

0 0

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Patent claims:

Claims (1)

- 20 patent claims 1 ·) Polymeric material compositions, consisting of 98 to 60 percent by weight of a polyvinyl chloride and 2 to 40 percent by weight of a solid product, which is obtained by polymerizing ethylene together with a monoethylene-like unsaturated compound, of which at least one of the free valencies by a monovalent radical of the formula - CN or -COOR, in which R is hydrogen or a monovalent hydrocarbon radical or by the divalent radical of the formula - CO - O - OC - is saturated / of which at least two of the remaining valences are bonded to hydrogen atoms » um to give a polymerization product * which contains 7 to 95 wt. units of the monoethylartlgenic unsaturated compound mentioned. 2.) polymers compositions of matter according to claim 1 characterized »» that it contains 5 to 15 wt -% of said solid product contained.. .. ■ 3.) Polymers St off compositions according to claim 1 or 2, characterized »that the solid product contains 15 to 75 wt .- ^ units of the monoethylene-like unsaturated compound mentioned. 4 ·) Polymeric substance compositions according to claim 1 »thereby characterized in that said Raonoäthylenartlge unsaturated compound is selected from the group of acrylic and Methacrylic acids, their esters and nitriles and malelic and 909806/0957 H94125 - 21 - ' Vuaftrsauren and their prayers 5 «) polymeric fabric compositions according to claim. 1 to 4" characterized in that the aonoathylenartlge unsaturated Compound is methyl methacrylate. 6.) Polymeric compositions of matter according to claims 1 to 5 characterized in that the aonoathylenartlge unsaturated Compound Xthylacrylate 1st. 7) polymeric substance compositions according to claim 1 to 6, characterized in that said solid product is obtained continuous is made by joint / polymerizing ethylene with the ge * called aonoäthylenartlgen unsaturated compound in a «RBhrautoclave · 8.) Polyaere compositions of matter according to claim 1 to 7 » characterized in that the polyvinyl chloride is brought into the Qelfora prior to mixing will. 909806/0957 KBl · ^Λ \ $ OS 5 0 £