DE2551014A1 - THERMOPLASTIC GRAFT MIXED COPOLYMERISATES AND METHOD FOR THEIR PRODUCTION - Google Patents

Description

The invention relates to a process for the production of thermoplastic graft copolymers, in particular a process in which the graft copolymers by heating a mixture of a basic copolymer, has the reactive sites, with a side chain polymer that is one with the sites contains reactive amino group. The invention also includes that according to this Process produced graft copolymers.

Numerous graft polymerization processes are described in the literature. In general, the term "grafting" refers to a two-stage process in which a polymerizable monomer is first mixed with a polymer and the monomer is then, for example polymerized by _(free radical or ionic graft polymerization in the presence of the polymer. In the conventional processes, the term " Grafting "a process by which

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Telephone: (0221) 234541-4 Telex: 88S 2307 dopa d Telegram: Dompatent Cologne

the side chain polymer in the presence of the "dead" or preformed polymer is generated. In the usual grafting process, irradiation with electrons, Treatment with peroxides, etc. to activate sites on the polymer chain for subsequent polymerization of the monomer and for grafting onto the active sites.

No prior art publication is used the production of a thermoplastic polymer by a process described in which a base copolymer a preformed side chain polymer that has an amino group reactive with sites on the base copolymer contains, is grafted. The method according to the invention has, inter alia, the advantage that two or, if desired, several types of side chain polymers on one base copolymer simply by mixing the preformed ones Polymer side chains can be grafted at the time the grafting reaction takes place.

In one feature, the invention is directed to the manufacture of thermoplastic graft copolymers directed a method, which is characterized in that one

1) a basic copolymer composed of at least two monomers, at least one of which is reactive with amino groups Positions in the form of an anhydride group, a vicinal pair of carboxyl groups and / or a carboxyl group, which is adjacent to an alkoxycarbonyl group, the alkoxy radical containing up to 20 carbon atoms and at least one of the monomers has no sites reactive with amino groups, and

2) at least one side chain polymer, one per chain reactive amino group selected from the primary and secondary Amines existing group contains, while the rest of the side chain polymer with the reactive

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Places the base copolymer is essentially unreactive,

Heated with mixing for about 15 seconds to 60 minutes. The composite graft polymer formed is thermoplastic and not networked.

According to a further feature, the invention includes those made by the method described above thermoplastic graft copolymers consisting of a base copolymer and at least one via amide or Imide bonds linked to the base copolymer Chain polymers consist of a short-chain polymer that has about 5 to 60 repeating units and contains a primary or secondary amino group usually at one end of the polymer chain while the remainder of the side chain polymer is with the sites reactive with the amino group of the base copolymer is essentially non-reactive. The amino group of the side chain polymer becomes during the grafting process to the active site of the base copolymer, i.e. to the anhydride group, the two vicinal carboxyl groups or the vicinal carboxyl and Älkoxycarbonylgruppen bound and provides the amide or imide nitrogen atom.

The term "base copolymer" used here denotes the polymerization product of at least one polymerizable monomer which is not reactive with amino groups Has sites, for example an α-olefin such as ethylene and a vinyl monomer such as vinyl acetate, styrene and vinyl chloride and at least one polymerizable Monomers that have sites reactive with amino groups, e.g., maleic anhydride. The term includes copolymers on which a monomer is grafted which introduces the sites reactive with amino groups, e.g. ethylene / α-monoolefin / 1,4-H6xadiene / maleic anhydric

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Copolymers. The base copolymer can, but does not have to be, elastomeric.

With the expression "side chain polymer" used here is the name given to the polymerization product of a polymerizable monomer that has an active amino site per chain usually at one end of the side chain poly- j

contains merisats. The other ends or substituents- ' groups of the side chain polymer are essentially non-reactive with the reactive sites on the base copolymer. The extent to which more than one reactive body per! Chain can be present depends on which in a particular one The degree of crosslinking achieved, i.e. the amount of additional that exceeds one reactive point per chain reactive sites per chain must be so small that the graft copolymer is not significantly crosslinked.

The expression "elastomer" used to characterize the base polymers means that when they are crosslinked they can recover quickly and vigorously from large changes in shape. That of extenders and thinners Free crosslinked base polymers stretch to less than 1.5 times within a minute their original length together after being stretched to double their length at 18 to 29 C, 1 minute held stretched and then relieved. However, these base polymers are used in the process according to Invention used in the non-networked state.

By the method according to the invention it is possible to add at least one type of side chain polymer to those with amino groups graft reactive sites of the base copolymer, however, two or more different types of sites chain polymers may be present in the graft copolymer. The term "various types of side chain polymers" denotes at least two side chain polymers, e.g. polycaprolactam, polylaurolactam, polyethylene oxide, poly-

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propylene oxide and other pages ι described below chain polymers which are used for the purposes of the invention

have different chemical structures. The term "various types of side chain polymers" denotes not just a difference in molecular weight of a particular type of side chain polymer, e.g. Polycaprolactam.

In the final graft copolymer, the base copolymer content is in the range from about 25 to 95% by weight and the content of side chain polymer in the range from about 5 to 75% by weight.

If the base copolymer is elastomeric and the proportion of the base copolymer in the final graft copolymer is about 45 to 85% by weight, that is final! term graft copolymer, also \ if neither the used nor the Grundcopolymerisat j obtained graft copolymer any further treatment, for example vulcanization or crosslinking, j is subjected also elastomeric. Above a proportion of 85% of the elastomeric base copolymer, the mechanical properties of the graft copolymer tend to deteriorate. The base copolymers contain, calculated as a number average, about 300 to 50,000, preferably 500 to 5000 chain atoms and an average of about 1 to 200, preferably 1 to 50 positions which are reactive with amino groups per 1000 chain atoms of the base copolymer. On average there is at least one active site per chain of the base copolymer. The side chain polymer is generally shorter than the base copolymer and has a length of about 25 to 1000 chain atoms, preferably about 30 to 300 chain atoms.

The base copolymers must be sufficiently stable to withstand the heating during the grafting of the side chain polymer to resist. They must also be free of hydro-

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xyl groups, primary amino groups and secondary amino groups be that with the graft sites reactive with amino groups with the formation of thermally stable crosslinking bridges, which cause a loss of the desired thermoplasticity, can react.

The sites on the base copolymers that are reactive with amino groups are introduced by monomers that are either polymerized in during the preparation of the base copolymer or grafted onto an existing polymer.

The copolymerization of a monomer that introduces the sites reactive with amino groups with other monomers is possible if the other monomers can be polymerized by customary free radical catalysis, α-olefins, Alkyl acrylates and methacrylates, conjugated dienes, other dienes, styrene, methyl vinyl ether, methyl vinyl sulfide, Acrylonitrile, vinyl acetate and vinyl chloride are known examples of suitable comonomers.

The free radical polymerizable monomers used to introduce the sites reactive with amino groups The basic copolymers can be polymerized into, often have the formulas

Il

/ ^C \ 0 XYO

X-C \ H I I M

(a) "O, (b) Vi-O-C-C = C-C-OH and

Ii

0 H

V-C-C (c) '

W-C-C-

■ η N.

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wherein X and Y are independently H, Cl, C ^ Cg-alkyl and phenyl with the proviso that one of the radicals X and Y must be hydrogen, W for H, C ^ CQ-alkyl, phenyl, naphthyl or substituted phenyl or naphthyl radicals which contain C.-CQ-alkyl, halogen or C ^ -C ^ o "alkoxy radicals, and V stands for a radical which contains C ₅ -C ₁ " -alkenyl and a copolymerizable double bond.

As the compounds representative of the formula (a), there are, for example, maleic anhydride and citraconic anhydride to call. The compounds representative of formula (b) include maleic acid, citraconic acid, Fumaric acid, mesaconic acid and monoesters of maleic acid and fumaric acid. As examples of connections, representative of formula (c) are alkenylsuccinic anhydrides, e.g., 3-ethenylsuccinic anhydride and 3-isopropenyl succinic anhydride. Itaconic acid, its anhydride j, are also suitable and their monoesters, but these compounds j do not come under the formulas (a), (b) or (c).

The copolymerization reaction to form the base copolymer, in particular an ethylene copolymer, can be carried out on most advantageous in a pressure reactor at one temperature from 90 to 25O ° C and a pressure of 1600 to 2200 atm. be performed. The polymerization temperature is preferably at about 145 ° C and the pressure at 1800 to 2000 atm. held. In general, the polymerization process carried out continuously, with that! Monomers, optionally a solvent, e.g. benzene, .and the initiator are introduced in a controlled amount and the reaction product is continuously withdrawn. A stirred autoclave such as that described in US Pat. No. 2,897,183 is suitable. As free radical forming Polymerization initiators are, for example, organic peroxides, e.g. lauryl peroxide and di-tert, -

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-δι

butyl peroxide, peresters such as tert-butyl peracetate and \ tert-butyl peroxypivalate, and azo compounds such as azobisisobutyronitrile.

As a representative basic copolymer is a random one Mention copolymer, which has a melt index of about 0.3 to 100 g / 10 minutes and essentially consists of polymerized ethylene, 7-methyl acrylate or ethyl acrylate and, per 100 g of polymer, there is 0.0025 to 0.077 mol of a monoalkyl ester of a 1,4-butenedicarboxylic acid, wherein the alkyl radical of the ester contains 1 to 6 G atoms, with about 0.64 to 0.80 mol in every 100 g of copolymer Units of the formula -CO- are included. Copolymers of ethylene, methyl acrylate and ethyl hydrogen maleate with This structure has, for example, the following compositions (in mol%):

Ethylene Methyl acrylate Ethyl hydrogen maleate 71.2 28.7 0.1 57.8 42.1 0.1 74.4 22.0 3.6 61.4 34.4 4.2

Another representative basic copolymer is an alternating copolymer which contains recurring units consisting essentially of -AB-, where B stands for ethylene units and A stands for units made up of at least one C 1 -C 6 -alkyl acrylate and an acrylic monomer which forms vulcanization sites having the above formula (a) or (b) are selected. The copolymerization is carried out in solution at -10 to about 200 C in the presence of a free radical initiator and BFg at pressures sufficient to keep the BF ₃ complexed with the alkyl acrylate (generally 0.7 to 703 atm).
7 an alkyl acrylate such as

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An important group of copolymers that cannot be produced with j free radical catalysts!

form the EPDM polymers, especially EPDM rubber j

i schuke. These are copolymers of ethylene, an α-olefin (especially propylene) and a monomeric diene. These copolymers are prepared using the loading I knew Ziegler catalysts or Koordinationskatalysa- \ factors that combinations of transition metal compounds (generally vanadium or titanium compounds such as VOC1 "VCL, vanadium triacetylacetonate and j titanium tetrachloride) with organometallic Reduktionsmit-: tel. n of groups I to III (e.g. alkyl aluminum chlorides | and bromides, lithium aluminum tetraalkylene and aluminum trialkylene). EPDM rubbers are produced by copolymerizing ethylene and propylene with at least one non-conjugated hydrocarbon diene, for example 1,4-hexadiene, 5-propenyl-2-norbornene, 5-ethylidene-2-nor-! bornene, 5-methylene-2-norbornene and dicyclopentadiene, such as | in U.S. Patents 2,933,480, 3,000,866, 3,093,620, 3,093,3 211,709, and 3,151,173. One of the double bonds is generally much less reactive than the other. The polymerisation of the diene then leads to a monomer unit which is less reactive! tive double bond in the side chain. After the copolymer has been formed, individual monomer units, for example monomer units of the above formulas (a) and (b), which have sites reactive with amino groups, can be grafted onto the EPDM polymer by thermal addition to the unsaturated side chains. A typical basic copolymer can be represented by the following formula, which illustrates the case of the addition of a single maleic anhydride group to an ethylene / α-monoolefin / 1,4-hexadiene copolymer:

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H H

t I

C-C- "

t ι

H CH, ₀

HC CH ₂ -HC -CH -

Here the wavy lines represent the polymer chain.

This structure can be obtained by mixing maleic anhydride with the ethylene / α-monolefin / 1,4-hexadiene copolymer is heated. The hydrocarbon copolymer can also contain small amounts of units of a directional Contain non-conjugated diene, as is the case, for example, with ethylene / propylene / 1,4-hexadiene / 2,5-norbornadiene copolymer as is the case with other copolymers described in US Pat. No. 3,819,591. =

Propylene is normally chosen as the α-monoolefin for the production of the elastomeric ethylene copolymers which are unsaturated in the side chain because of its availability and low cost. Higher α-monoolefins (C ₄ -C ^ o), for example! -Butene, 1-hexene and 1-dodecene, are also suitable. The α-monoolefins can be completely omitted, an ethylene / hexadiene copolymer being obtained. ·

The graft addition of the above-described, with Monomers reactive with amino groups, e.g. maleic anhydride and ethyl hydrogen maleate, are expediently carried out, by adding a mixture of the copolymer and the monomer reactive with amino groups to a range of about 225 to 400 ° C and above the melting point of the base copolymer and side chain polymer is heated. A procedure of this type will be described in detail in U.S. Patent 3,884,882. Internal mixers or extruders are suitable. The action of

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Maleic anhydride fumes on staff must be due _; largely eliminated its toxicity and the possibility of serious ί damage to the eyes

will. Unreacted maleic anhydride can be obtained from j

the graft polymer by extraction with water or!

by dissolving in hexane, a non-solvent for Maleih-!

acid anhydride. ;

In the production of the base copolymers can i a-olefin and the diene be omitted entirely, so> that ethylene and ethylenic monomers having functional \ carboxyl groups are copolymerized, wherein the comonomer mers j are linked via carbon-carbon bonds randomly with one another and the resulting copolymer ! sat contains 70 to 99% by weight of ethylene. Examples of such basic copolymers and related basic copolymers are: ethylene / maleic anhydride, ethylene / C ₁ -C ₄ monoalkyl maleate, ethylene / C 1 -C 4 monoalkylene fumarate. Ethylene / -C-, -Ch-monoalkyl itaconate. Ethyl acrylate / maleic anhydride, ethyl acrylate / monoethyl fumarate, styrene / maleic anhydride ¹ , styrene / Cj-C.-monoalkyl maleate, styrene / C.-C.-monoalkyl itaconate, alkyl vinyl ether / maleic anhydride, vinyl chloride / maleic anhydride and other copolymers containing 3 and 4 components, For example alternating ethylene / ethyl acrylate / aluminum acrylate / maleic anhydride copolymers, alternating ethylene / ethyl acrylate / ethylene diacrylate / maleic anhydride copolymers, ethylene / maleic anhydride / 3-methylbutene or vinyl acetate copolymers, monoumarin or vinyl acetate copolymers / monoumarate monomers, or vinyl acetate monoumarate monomers, or vinyl acetate monoumarate monomers, or vinyl acetate monomers / Butyl acrylate / monoethyl fumarate copolymers and vinyl chloride / vinyl acetate / maleic anhydride copolymers.

The side chain polymers grafted onto the reactive sites can be of the same type or belong to different types of polymers are mentioned below. As. Examples of side chain

_> ί

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polymers that can be grafted onto the reactive sites are:

1) Polymers of lactams with 3 to 12 carbon atoms, e.g. polycaprolactam, polylaurolactam and others Lactams,

2) Copolymers of these lactams with 3 to 12 carbon atoms, e.g. copolymers of caprolactam and laurolactam as well as other lactams,

3) Polymers of organic oxides with 2 to 16 carbon atoms, e.g. ethylene oxide, propylene oxide and dioxolane,

4) copolymers of the organic oxides mentioned with 2 to 16 carbon atoms,

5) polymers of styrene,

6) polymers of substituted styrenes (1 to 4 carbon atoms),

7) copolymers of styrene and substituted styrenes,

8) Polymers of acrylates,

9) polymers of methacrylates,

10) Copolymers of acrylates and methacrylates and

11) Polymers of lactones.

The graft copolymers according to the invention can be represented by the formula V ₁ W ₁ XYZ. Here in

k 1 m η ρ

V is the predominant monomer, W the modifying one Monomers for the basic copolymer, X the monomers containing the reactive sites, Y those in a side chain type repeating unit used and Z the repeating unit used in another type of side chain.

The graft copolymers can be prepared by a three-stage process in which a) V, W ₁ X is formed

ic χ m

will, b) Y and / or Z are formed and (c) the product ^v _k ^w ₁ ^x _m ^Y _n ° der V ^ ₁ X ₀₁ Y _n Z by a simple reaction

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- 13 - I.

tion is formed in the molten phase or solution.

If the value of the index k is greater than the value of the j index 1, the monomer V is regarded as the predominant monomer I. The value of the index 1 can even be 0. j W is considered to be so general that there is an or
comprises several modifying monomers. X is the mono; mere that introduces the reactive site. Y is the monomer from which the side chain polymer is formed,

I that can be a copolymer or a homopolymer. ^:

Y contains a primary or secondary amino group, and j generally at one end. Essentially none of the molecules Y contains more than one amino group or

other groups associated with the one associated with the monomer X ¹ -

i th reactive site are reactive because the; The reaction taking place in the melt would then form a crosslinked product. I.

According to an important embodiment, the process can be used to prepare graft copolymers of the formula
V, XZ to produce, in which V for ethylene, ethyl acrylate, styrene, etc., X for a functional ethylenic compound, for example maleic anhydride, monoalkyl acrylate with 1 to 4 carbon atoms in the alkyl radical, fumarate and itaconate; stands, V. and X are randomly linked to one another via CC bonds i, Z is a polyamide side chain of the formula:

0 0

Il "

N (CH ₂ ) _r C * NH (CH ₂ ) ^

^R 2

is, Z through an amide or imide group bond to X
is bonded, R ^ is hydrogen, or C ^ -C ^ -alkyl, Rp
for C 1 -C 3 -alkyl, aralkyl, e.g. benzyl, or aryl, e.g.
Phenyl or R 1 and R 1 together form a 5- or 6-membered ring; k, m, ρ and r integers are i

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(although the analyzes may give fractional average values for k, m and ρ), where the ratio of k: m ranges from 4: 1 to 200: 1, and k and m have such an additional relationship that the weight ratio of V ₁ : X ranges from 99: 1 to 70:30; km

r stands for 3 to 11, preferably for 5 to 11, and ρ

in the range from about 4 to 29, preferably from 5 to 9

lies. The value for r is decisive for the type of polyamide used.

The indices k and m in the above formula give the number of monomeric ethylene, acrylic or styrene units ^!

or the number of monomer units introducing the active site, e.g. maleic anhydride, in the base copolymer. Obviously no more than one Polyamide segment is bound to any X site, but not every X site need have a Y side chain.

When a polyamide is used as the side chain polymer, the amount by weight of the polyamide component depends on several factors, e.g. the frequency with which side chains are grafted on, the number of units per side chain and by molecular weight per unit .; The proportion of the polyamide side chain is generally in the range from 15 to 75% by weight of the graft copolymer. The proportion of polycaprolactam is generally in the range from 20 to 75% by weight, preferably in the range from 33 to 50% by weight of the graft copolymer, the elastomeric graft copolymers of polycaprolactam with the best mechanical properties, for example Contain 26 to 35.5 wt% polycaprolactam and those with the highest tensile strength about 33 to 47.5 Contain weight percent polycaprolactam, and the proportion of polylaurolactam is generally in the range of 15 to 60% by weight, preferably in the range from 15 to 35% by weight.

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The preformed side chain polyamides are preferably derived from oligomeric polycaprolactam or polylauro-1-actam or copolymers of these lactams. These oligomeric polylactams contain a reactive terminal primary amino group and a non-reactive end group. They are prepared by heating the lactam with an amine of the formula R _-1 NHRp, where R ₁ and Rp are H, C ₁ -C ₁ "-alkyl, benzyl or C, -C, - cycloalkyl with the proviso that R ₁ and Rp are not both hydrogen, and R ₁ and Rp together form a ring such as in C.-Cc-alkylene or a ring which contains a heteroatom such as, for example, in 3-oxapentylene, in an amount selected in this way is that an oligomer with a predominantly middle! Degree of polymerization in the range from about 5 to 60, before | preferably 6 to 10, in particular 6 to 8, is formed. This reaction, which is carried out at a temperature in the range from about 250 to 300 C, can be based on theory on a quantitative basis as follows:

.C = O

(CiH ₂ ) /

"" NH

H [NH (CH ₂ ) _r 0] _p N.

Here, R ^, Rp, r and ρ have the meanings given above.

Optionally, a small amount of water can be added as a reaction accelerator. In this case a terminal free carboxylic acid group in a small amount corresponding to the amount of water, as an alternative formed to the terminal amido group. It is possible that the reaction does not proceed quantitatively in practice, as the product is unchanged lactam and amine and a small amount of a mixture of oligomers with

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May contain degrees of polymerization below 5. Since the unchanged starting materials and the lower molecular weight oligomers are readily soluble, they can be removed by solvent extraction and the remaining oligomeric mixture can then be used to prepare the graft copolymer. This possibility of adjusting the quality of the side chain polymer is an important advantage of the invention. The average polymerization degree of the remaining polylactam is by analysis by conventional titration for terminal amino groups as equivalents per G _e of the sample weight unit determined.

The graft copolymers can according to various Process are produced. Convenient methods described herein can be denoted as follows: j will: ;

1) The anhydride process for use with ethylene / maleir Acid anhydride and other basic copolymers containing anhydrides, and

2) the route via vicinal acid groups or via a vicinal Pair of acid group and ester group for use in basic copolymers containing a dicarboxylic acid or a monoester of vicinal dicarboxylic acid substituents contain.

The anhydride process that is preferred becomes simple the basic copolymer which contains carboxylic anhydride groups, preferably maleic anhydride, and the amino oligomer in the molten state to a temperature in the range of from 75 to 250 ° C, preferably heated to about 225 ° C, or in solution to a temperature of 75 to 100 ° C or above with mixing. The temperature, to which is heated is above the melting point of the base copolymer and the reactive polymer! sats. The reaction time, which depends on the temperature and the

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Depends on intensity of mixing, may be in the melt j about 15 seconds to 60 minutes, preferably 1 to j 10 minutes and in solution for 15 seconds to 5 ^hours,: preferably 1 to 10 minutes, respectively. The reaction I in the melt, a particularly preferred process, j can expediently on a roller mixer, in one
Melt extruders or in internal mixers with spiral rotating bodies, Sigma blades, etc. at a temperature at which the reaction time is short, and with; so many passes that ensure complete- | diger reaction are necessary to be carried out. \ Whether the reaction is complete can be judged by the appearance of j

ι of the product can be assessed. Good clarity in the melt is an indication of an essentially complete reaction. When using a roller mixer j as the reactor, the main chain copolymer and the oligomer can be premixed or mixed during the reaction on the roller mixer. It can be advantageous ^: to add stabilizers, for example inhibitors or antioxidants, or to carry out the reaction in a protective gas atmosphere, for example nitrogen. When using an extruder as a reactor, it is advantageous to use the
Premix ingredients. Based on the infrared analysis of the products, it is assumed that the thermal reaction proceeds from the initial formation of amic acids to the eventual formation of
Amide or imide bonds run between the main chain copolymer and the polyamide side chains,
eg:

+ H ₂ N-

-C

.0

-C

NH-

-C -C

N- + H ₂ O

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The amount of the amino oligomer used may vary depending on the degree of side chain substitution desired vary on the graft copolymer from less than stoichiometric to stoichiometric.

The route via vicinal acid esters generally has the same process features as the anhydride process, i.e. the process can be in solution or in the melt during a reaction time similar to that above

anhydride process described is to be carried out It is assumed that the graft copolymer}

by polymerizing the oligomeric polyamide side chain on the "Kettenrückgraf" copolymer via imide bonds (with the excretion of alcohol), caused by the intermittent formation of amino acids, (amic acids) ζ.Β

-C

-C

'OR .OH

.0 's MtH- .OH -C -C

-c

+ RAW

H ₂ O

or by prior conversion of the vicinal acid ester to an anhydride and by loss of alcohol Reaction of the latter with the amino oligomer can be formed in the manner described above. The above description of the anhydride process carried out on a roller mixer] or in an extruder also applies to the process carried out in the same way via the vicinal acid-ester pair.

The reaction of the amino group with the anhydride proceeds fast, so that the effective reaction rate of the polymers containing these groups through other factors, such as the speed or intensity of mixing, are limited. When two polymers dissolved separately in solvents and the two solutions

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be cast together gen, fast intimate ·, mixing takes place. The reaction in solution can be completed in about 1 minute or less at about 100 ^° C.! be guided. Can ι with increasing temperature of the solution, the reaction in less than 1 minute, to be [15 seconds terminated eg.

When the two polymers are mixed in the melt!. they are generally incompatible before the reaction takes place. The mixture consists of two ₍ incompatible liquids, and the reaction takes place primarily at the interface. As the reaction progresses, the mixture of the melts changes into a single phase, and the reaction continues even at temperatures of the melt of only about 100 ° C) . very quickly to the end before completion of the grafting reaction, are mixtures of the carboxyl-containing ^main: chain copolymers and the amino-containing oligomeric polyamides in the melt characteristic!

cloudy. In contrast to the graft copolymers by extraction with suitable solvents into the main chain copolymers and the lactam oligomers be separated. '

The graft copolymers are produced by the chemical reaction of the. reactive point of the basic copolymer identified with the active amino group of the side chain copolymer. This can be demonstrated by it is demonstrated that the reactive site on the base copolymer with the formation of any other chemical unit has reacted. In the special case of the anhydride group, the reaction can be carried out with the aid of known Analytical methods are proven.

For example, the progress of the grafting reaction can be followed by infrared spectroscopy. If that Base polymer used - active sites in the form

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contains five-membered cyclic anhydride groups, the disappearance of one of the two characteristic absorption bands at 5.4 u or at 5.6 u is a sign that the grafting reaction is taking place. The proportion of anhydride groups in the base polymer used can be determined by forming a polymer film of known thickness and examining the infrared spectrum of this film. It has been found experimentally that 11 absorption units / mm at 5.4 μ or 87 absorption units / mm at 5.6 η correspond to 10% by weight of anhydride. The absorption units are read directly from an infrared spectrogram.

The characteristic infrared absorption band lies in a similar manner at 5.9 u, if the basic copolymer used has vicinal carboxyl and alkoxycarbonyl groups contains. Assuming that the vicinal carboxyl and alkoxycarbonyl groups of ethyl hydrogen maleate are to be derived, the characteristic absorption is 43 absorption units / mm per 10 wt .-% of the existing maleate. These analytical methods would be in the case of a starting copolymer containing vicinal carboxyl groups not applicable. However, the concentration of the carboxyl groups can be determined by simple Easily determine titration.

The graft copolymer formed as a product can by various methods that the presence of Polyamide side chains, the degree of polymerization of the polyamide side chains and the chemical identity of the polyamide prove - to name just a few - are characterized. Certain physical properties are also often useful in demonstrating that a graft copolymer has been formed.

The presence of polyamide is due to infrared absorption detected at 6.0, u (amide carbonyl). Other

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useful wavelengths are 6.4 η (-NH bending) and j 3.0 u (-NH stretching). The proportion of the polyamide is j

by Kjeldahl analysis for percentage nitrogen

I definitely do. I.

The polyamide can be identified chemically by
a sample of a graft copolymer with an i

Mineral acid, e.g. sulfuric acid or hydrochloric acid! about 200 ⁰ C or more is heated. Under these conditions, the polyamide chain is broken down into the starting lactam. Since £ -caprolactam and cd -Lauro.lactam are volatile, they can be isolated and identified by any suitable j method of qualitative analysis, j

A direct measurement of the grafting efficiency by extraction of unbound polyamide is difficult: since most solvents for polyamides also include the j graft copolymers and also most basic j attack copolymers. The titration of the graft copolymer for reactive functional groups gives j no more than rough estimates of graft efficiency.

Determining the increase in molecular weight due to grafting is a convenient method. These
Determination is usually made by gel permeation chromatography of 0.5% solutions of the graft copolymer in m-cresol at 100 ⁰ C on columns, which are filled with porous polystyrene.

A good indication that grafting has taken place
has is the torsional modulus of the product, in particular

at 100 to 150 ° C. While the polyamide graft mix

7 8
polymer has a fairly high modulus (e.g. 10 -10

2,

Dyn / cm), the ungrafted material flows into

this temperature range.

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The graft copolymers are identified as such and not as mere mixtures of the basic copolymers and the polymers of the side chain type with the aid of various tests. These include the clarity of the melt, the solubility properties and, in certain cases, the extent to which they retain their modulus of elasticity at elevated temperatures. Mixtures of the two polymers or of a polymer with an oligomer are generally not compatible. Molten mixtures generally consist of two immiscible phases. These two-phase systems are cloudy due to the difference in the refractive index between the two types of polymer. If such a system changes from an opaque or cloudy product to a clear product, this is strong evidence that a graft polymer has been formed. The same optical test can be applied to samples in sheet form, in the solid state at room temperature. | Another well-known method of distinguishing; connection between a mixture and a graft polymer \ based on the different solubility of the candidate types of the polymers. A third method is based on the extent to which the polymers retain their physical properties at elevated temperatures. With these types, the mixture tends to lose its rigidity and flow as the temperature rises. Certain graft copolymers retain their rigidity better and better with increasing temperature

crawl less.

In the case of polyamide graft polymers, where the middle Degree of Polymerization (DP) each as a starting material a-j set side chain polymer is known, it is possible to adjust the degree of polymerization depending on the! determined with a differential scanning calorimeter (DSC) ' maximum melting point of each graft copolymer formed

609821/0917

merisats graphically. It was determined,! that the maximum melting point increases with increasing degree of polymerization of the side chains. Such a graphical representation can serve as a calibration curve for
Determination of the degree of polymerization of the grafted side chains in the copolymers according to the invention 'can be used. i

Before the test, the polyamide-graft copolymer. Risate can be conditioned by first heating it to 250 CJ and then cooling it to 50 C at a rate of 10 C / J minute. During the test will
the sample is heated at a rate of 10 C / minute. !

Determination of the melting point with the differential scanning calorimeter is described in "Thermoanalytical Methods, of Investigation" by P.D. Garn, Academic Press, New York

1965, described. j

Another useful and somewhat related method, j the degree of polymerization of the grafted polymer! side chain correlated with their melting point
to bring is the differential thermal analysis
(differential thermal analysis = DTA). The rehearsal must
are also preconditioned and will be used during the
Tests heated at a rate of 20 ° C / minute. The details of the DTA method are given in "Differential Thermal Analysis" by RC MacKenzie, Academic Press,
New York 1970, particularly in Chapter 23 of CB.
Murphy Treating Polymers, Volume I, pages 643-671.

It should be noted that the above-described
Identification methods based on the determination of the
Melting point of the polymers are based, ie the DSC
and DTA methods, are only applicable to polymers with a high degree of crystallinity. With an elastomer

609821/0917

Basic copolymers with low crystallinity only have crystalline side chains, especially polyamide side chains, well-defined or sharp melting points which are recorded. If the basic copolymers! have a fairly high crystallinity and contain, for example, a high proportion of ethylene, your! Crystallinity must be high enough to develop a pronounced melting point maximum. However, this lies well below the temperature range of interest and does not interfere with the determination. If two or more different crystalline side chains, e.g. a polycaprolactam and a polylaurolactam are present, there is a corresponding number of melting point maxima on the DSC or DTA recording. The polyamide graft copolymers have a crystalline basic copolymer and have a corresponding DTA melting j point at 80 to 115 ° C. The other melting point is at least 165 ° C. if only polycaprolactam side chains are available, and at least 150 C! if only polylaurolactam side chains are present.

The flexural modulus is another property that distinguishes between the plastic ones described here Graft copolymers of elastomeric graft copolymers enables. The factors that affect flexural modulus are not just about the difference in the components and the amount of each component present, but also the length of the side chain poly — j

2 merisate. Below a flexural modulus of around 1969 kg / cm,

i at room temperature are the graft copolymers

I elastomer, while above this value they are plastic. However, there is no sharp dividing line in the flexural modulus between plastic and elastomeric, especially when "the polyamide content is 50 wt -.% Polyamide approaches At lower concentrations, for example 25% and less, is the.

609821/0917

25510H

- 25 - '

Flexural modulus of elastomeric graft copolymers _: well below 1968.6 kg / cm. If the basic copolymer! sate of plastic graft copolymers according to the j invention at temperatures below their crystal; Melting points cold stretched and before discharge; If they are held stretched for 1 minute, they are oriented; and do not recover significantly from the change in shape within a period of 1 minute. In contrast to this] the elastomeric basic copolymers are drawn within,

the ί

half a minute to less than / 1.5 times their original length after they were stretched to double their length at 18 to j 29 C and before the
Relief have been held stretched for 1 minute.

The method enables setting and regulation [ of the type and length of the polymer side chain that are related to the
Basic copolymer is grafted. From the special ^: type of base copolymer can be the average; borrowed frequency of possible reactive grafting sites j due to the proportion of monomer molecules that form the reactive sites and are polymerized into the basic copolymer! be easily determined. As the polymer
Side chains before the reaction with reactive sites! The basic copolymer are formed, any desired graft copolymers can be easily produced. For example, a polymer side chain with; narrow or broad molecular weight distribution formed! will. The polymer side chains with the most diverse
Distributions can be formed at different times and then grafted on at different times.
It is possible to have two or more different types of
Grafting on polymer side chains using the method. The thermoplastic graft copolymer obtained is essentially not contaminated with non-grafted side chain polymer, which is the case with
the usual free radical graft polymerization

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25510H

can be big problem.

To achieve improved high temperature properties it can be useful that the side chain polymers have a length such that these side chains can crystallize. A certain type of side chain can be used to achieve good antistatic properties However, it may also be important to keep its length below the value of the one would cause substantial crystallization at room temperature. One such case is with polyethylene oxide side chains before. If the side chains of such a polymer contain more than 80 chain atoms, The side chains crystallize at room temperature and lose their good antistatic behavior.

The graft copolymers can have selected physical properties that are suitable for molded parts such as | suitable for elastomeric and flexible foils and hoses! make, be made. The graft products can - | characteristic way their modulus of elasticity at |

Preserve elevated temperatures, a feature that the uses of foils, hoses and pipes expands into temperature ranges in which molded parts made of mere mixtures of polyethylene and polyamides ι have been manufactured, fail and fail. Good toughness (impact resistance) at low temperatures can also be achieved. For certain applications e.g. in hoses for automobiles, resistance to zinc chloride is extremely desirable. Graft copolymer! Risates with polylaurolactam side chains proved to be particularly resistant to zinc chloride. Another A surprising property of considerable value is the reduced water absorption by the graft copolymers compared to materials such as homopolycaprolactam (nylon-6) or mixtures of nylon-6 with polyethylene exhibit. The elastomeric graft copolymers

603821/0917

Risate according to the invention can be used for overmolding wire, for the production of hoses, belts, tapes,!

Straps, pressed shoes and boots and seals |

ι be used. You can go to low pressure tires for i

slow all-terrain vehicles and through melting; spin to be processed into elastic threads. i

The graft copolymers are suitable for production _; of various molded parts. In particular, j graft copolymers, for example those which have side chains; contain from Polyäthylenoxyden, in a _{hydrocarbon-t} stoffpolymerisat, for example polypropylene, incorporated

i, whereby polypropylene fibers, which to a large extent j

are antistatic. For the production of a hot melt adhesive, ethylene graft mix | polymers are mixed with relatively low molecular weight thermoplastic resins. It has I demonstrated that the adhesive is resistant to breakage at elevated temperatures ratures to a greater extent than an adhesive based on non-grafted ethylene copolymers. The grafting of a polymethyl methacrylate side chain onto rubber-like copolymers, e.g. ethylene / vinyl acetate copolymers, is an agent for modifying hard vinyl chloride base polymers.

Examples

The invention is illustrated by the following methods and examples in which the quantities are given in percentages and parts are by weight.

The physical and / or chemical properties of the copolymers used as starting materials were determined as follows -!:

a) The inherent viscosity in dl / g was measured at 30 ° C with a solution of 0.1 g of polymer in 100 ml of chloroform.

609821/0917

b) The neutralization equivalent was determined by acid-base titration determined using aqueous sodium hydroxide standard solution, the anhydride titrated as dicarboxylic acid.

c) The Wallace plasticity at 10O ⁰ C was determined by the following method:

Wallace plasticity is a measure of the degree of flow or deformation of uncured I elastomeric materials under load. The sample to be tested is rolled out to form a fur and a granulate Thickness in the range of 3.18 to 7.6 mm (0.125-0.300 inches) cut. The test is carried out with a Wallace— Piastimeter developed by H.W. Wallace and Co., Ltd., London. First, the test specimen is during a time of 15 seconds to exactly 1 mm height together- '; printed and heated to 100 C. Then the test grain exposed to a load of 10 kg for exactly 15 seconds at 100 C. The final thickness of the specimen, expressed in units of 0.01 mm, the plasticity is a value.

d) The melt index was at 190 C under load of 2160 g according to the method ASTM D 1238-63, Condition E or Condition A, measured and then for Condition E converted into an equivalent value.

The degree of polymerization (PG) or the molecular weight the 6-nylon used as the starting material can be easily determined by analyzing the end groups. the Terminal amino groups are determined by titration with a strong acid either in the presence of an indicator or determined by a potentiometric method or conductance measurement method. Terminal acid groups are determined by titration with a strong base. These methods are described in "Nylon Plastics" by M.I.Kohan, 38 and 105, John Wiley and Sons, New York 1973,

609821/0917

and j in "Encyclopedia of Polymer Science and T _e chnology" Volume 10, page 542 and 543, John Wiley and Sons, New York 1969 j described. j

The elongation at the yield point, the tensile strength at the yield point in psi (kg / cm) (yield point), the
Elongation at break and tensile strength in psi (kg / cm2)
are measured according to the ASTM D 638-72 method. :

i The flexural modulus is measured according to ASTM method D-790-71 j. The specimens are in at 190 to 220 C
pressed a laboratory press or by injection molding in the form of rods 1 127 12.7 χ j 3.175 mm in size. The bars are before the exam

i conditioned for 16 to 24 hours at room temperature. I The test is carried out with a measuring length of 5.08 cm at a ·. Speed of the pulling clamp of 1.27 mm / minute j performed. The flexural modulus (tangent modulus of elasticity) is calculated using the equation given in the ASTM standard. D _e r j obtained

2 '

The value is expressed as the flexural modulus in Ib./sq.in. (kg / cm).

The notched Izod impact strength (Izod) is based on the
ASTM method D 256-73 determined. The test specimens are
by injection molding at 285 ° C in the form of rods a
Manufactured in size from 127 χ 12.7 χ 3.175mm. the
Test specimens are notched and cut to length,
as prescribed in ASTM D-256-73. The samples are
after cutting and notching and before testing 16
conditioned for up to 24 hours at room temperature. from
Five test bars are tested for each sample. The average value is expressed as the notched Izod impact strength in
ft.lbs./inch notch (mkg / 'cm notch) stated.

609821/0917

25510U

Production of basic copolymers (processes A to U)

A. Production of an ethylene / methyl acrylate / monoethyl maleate copolymer

A terpolymer containing 46.4% ethylene, 50% methyl acrylate and 3.6% by weight monoethyl maleate and one Melt index of 3.6 g / 10 minutes was in a stirrer autoclave with a capacity of 0.72 1 produced.

A mixture of methyl acrylate, monoethyl maleate and ^: benzene (weight ratio 68.28 / 2.46 / 29.26) was I.

2 '

brought under a pressure of about 422 kg / cm. Separately from this, ethylene was subjected to a pressure of about 422 kg /

2 '

cm brought. Separate streams of this mixture (0.91; kg / hour) and the ethylene (6.35 kg / hour) were mixed \

2 and brought under a pressure of 1900 kg / cm. ! The resulting feed stream was then introduced into the autoclave. At the same time, a catalyst solution, | by adding 50 ml of tert-butyl peroxypivalate to j

4.5 kg of benzene had been produced at a rate of 0.00204 kg / hour at which the temperature was 170 ° C | was held, introduced. The product emerging from the autoclave was passed through a pressure relief valve into a chamber under normal pressure, where most of the remaining monomers and the solvent were evaporated off. That is iso-! Lated ethylene / methyl acrylate / monoethyl maleate terpolymer was freed from the small amount of residual volatile constituents by soaking in flowing! Nitrogen was kept at 80 ⁰ C. Acid-base titration indicated that there were 0.25 milliequivalents of acid groups per gram of the terpolymer. This corresponds to 3.6% by weight of the monoethyl ester of maleic acid.

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25510H

B. Production of an ethylene / vinyl acetate / maleic anhydride copolymer

A terpolymer containing 60.3% by weight of ethylene, 38% by weight of vinyl acetate and 1.7% by weight of maleic anhydride and had a melt index of 220 g / 10 minutes was used in an amount of 0.68 kg / hour. in one continuous; working 0.721 agitator autoclave as follows represents: The monomers were mixed, placed under a pressure of 1900 kg / cm and in the following; Quantities supplied::

Ethylene 4.54 kg / hour j

Vinyl acetate 2.29 kg / hour j

Maleic anhydride 0.015 kg / hour j

At the same time, a solution from Azobisisobutyro— |

nitrile in benzene supplied in such an amount that j

the reactor ^{temperature was kept at 170 0} C (about I.

0.587 g / hour corresponding to 0.86 kg catalyst / 1000 kg j

Terpolymer). The benzene was in a total!

of 1.04 kg / hour introduced. The terpolymer formed - j

risat was carried out in the procedure described under "Procedure A"

Way isolated. The proportion of maleic anhydride '

was 1.7 wt%. I.

C. Production of an ethylene / vinyl acetate / maleic acid / anhydride copolymer ;

A terpolymer that contains 65.6% ethylene, 32% vinyl acetate! and contained 2.4% maleic anhydride and had a melt index of 125 g / 10 minutes, was used in an amount; of 0.63 kg / hour produced in a continuously operating \ 0.72 1 stirrer autoclave as follows: The j monomers were mixed under a pressure of 1900 ί

2 '

kg / cm and supplied in the following quantities:

Ethylene * 4.54 kg / hour

Vinyl acetate 1.80 kg / hour

Maleic anhydride 0.0258 kg / hour

609821/0917

2551

At the same time was a solution of azobisisobutyronitrile

in benzene in such an amount that the reactor temperature was kept at 170 ° C. (about 1.00 g / hour corresponding to 1.58 kg / 1000 kg terpolymer). The benzene was added in a total amount of 0.67 kg / hour. introduced. The terpolymer 1 was isolated as described under "Method A" way \. Acid-base titration with aqueous sodium hydroxide standard solution showed that 0.49 milliequivalents j dicarboxylic acid, which was derived from the anhydride groups, were present per gram of terpolymer. The ■

The proportion of maleic anhydride was 2.4% by weight. !

D,., Production of an ethylene / ethyl acrylate / allylacry- · |

lat / maleic anhydride tetrapolymer

In a 7.57 T stirred autoclave were under nitrogen 4000 ml of methylene chloride, 400 g of ethyl acrylate,! 20 g maleic anhydride, 1.2 g allyl acrylate and 1.0 g j Azobisisobutyronitrile introduced. The autoclave was'

then closed and after introducing 300 g of boron

trifluoride with ethylene to 21 kg / cm. the subsequent copolymerization at 25 C was carried out until the pressure measurement showed that the uptake of Ethylene had stopped (about 2 hours later). The reaction was terminated by adding 1 liter of diethyl ether. Volatiles were removed by steam stripping under a well ventilated hood. The tetrapolymer obtained in this way was dissolved in acetone, precipitated in water in a mixer and dried in the oven. The yield was 415 g.

This product contained about 50 mole percent ethylene units and was slightly branched through the use of the directional allyl acrylate. The polymer chain consisted mainly from - (E) - (B) units, where E stands for ethylene and B arbitrarily from ethyl acrylate, allyl acrylate and maleic anhydride is selected (2.5% by weight).

609821/0917

D _,? , Production of an ethylene / ethyl acrylate / ethylene j ^ ' diacrylate / maleic anhydride tetrapolymer j

The above-described process D, .. was repeated with the difference that 1.2 g of ethylene diacrylate _{(were used} in place of allyl acrylate. The yield was 479 g. The branched tetrapolymer obtained contained about 50 mol. The ₍ polymer chain consisted mainly of units i - (E) - (B ¹ ) -, where E stands for ethylene and B 'is arbitrarily selected from ethyl acrylate, ethylene diacrylate and maleic anhydride (3.8% by weight).'

D, _. Production of an ethylene / ethyl acrylate / ethylene-! diacrylate / maleic anhydride tetrapolymer 1

The procedure described above D, ^% was again;

- I.

with the difference that 0.75 g of ethylene diacrylate! were used in place of the allyl acrylate and the amount of maleic anhydride was increased to 30 g. j The yield was 417 g. The branched tetrapolyme- ^! Risat contained about 50 mol% ethylene units, which were arranged as follows, just as with D / ">:
- (E) - (B ¹ ) -. The proportion of maleic anhydride was
3.9 wt%.

D-.v mixture of branched alternating copolymers! ^K ' risaten . ^:

According to the method D, ^ s, D / _? \ and D,., .. produced branched copolymers were mixed on a roller mixer. The properties of the mixture and its
Ingredients are listed in Table I below.

609821/0317

Parts in
mixture Table I. Copoly-
merisat
D. 397 Inherent
Viscosity (1) 479 1.91 (2) 417 1.33 (3) 1.21 mixture (4) 1.75

(a)

Wallace-Neutralisa-Plastizierungsequivatät lent

Milliequiva lent / q

16.8

15th

15th

14th

0.52 0.77 0.80

0.70

(b)

(a) dl / g; measured at 30 C on a solution of 0.1 g
Copolymer in 100 ml of chloroform.

(b) Acid-base titration using aqueous sodium hydroxide: standard solution, the anhydride j

titrated as dicarboxylic acid. Maleic anhydride content 3.4% by weight.

E. Production of an ethylene / ethyl acrylate / allyl acrylate /! Maleic anhydride tetrapolymer

I The experiment was carried out as in Part D, - ν with the i

2 i

Difference that the ethylene pressure was 42.2 kg / cm. j The yield was 233 g. The tetrapolymer had | an inherent viscosity of 2.37 dl / g, a Wallace- j plasticity of 24.4 and a neutralization equivalent j of 0.49 milliequivalents / g. 2.4 wt% maleic anhydride was present.

^F (l) (2) ^{Production of} ethylene / ethyl acrylate / allyl acrylate / maleic anhydride tetrapolymers

The one in Part D.

(1)

The experiment described was carried out twice

repeated with the difference that the amount of
Maleic anhydride reduced to 10 g in both cases
became. The yields were 481 g and 497 g, respectively. At the
Run F,, were 1.8% by weight maleic anhydride and

when trying F
send.

₍₂ )

^G ew .-% maleic anhydride applicatio

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25510H

F, _. Production of an ethylene / ethyl acrylate / ethylene- ^ diacrylate / maleic anhydride tetrapolymer

The experiment described in Part D, ... was repeated with the difference that 0.75 g of ethylene diacrylate was used instead of allyl acrylate. The yield was 476 g. 2.3 wt% maleic anhydride was present.

F,., Preparation of mixtures of branched copolymers

A basic copolymer mixture was prepared by mixing the copolymers F,. ^, F, ". and F, ₃ v made on a rubber [ roller mixer. The characteristics are given in Table II below. ]

Parts
in Ge
mix Table II Wallace
plasticity 1
Neutralisa— _;
equi— i
valent;
Mil 1 iäquiva-i
lent / q component 336
292
2 ul Inherent
Viscosity 15.5
13.3
Ik
I3.5 O.36!
O.U2;
O.kS !
o.itfte) ^F (D
^F (2)
⁷ O)
mixture
F, .. 1.97
I.78
1.52
IW *

(4)
a) 2.1% by weight maleic anhydride was present.

G. Production of an ethyl acrylate / monoethyl fumarate ·! - copolymer

In a three-necked round bottom flask, nitrogen was passed through a mechanically stirred mixture of 500 ml of benzene for 30 minutes. 100 ml of inhibited ethyl acrylate, 7.2 g of monoethyl fumarate and 0.25 g of azobisisoburyronitrile, whereupon the mixture was kept under nitrogen at 50 ° C for 24 hours became. The copolymer was isolated by steam distillation in a well-ventilated hood and over

609821/0917

25510H

Dried overnight in a vacuum oven with nitrogen circulation (nitrogen — bled vacuum oven) at 7O C » The conversion was 86%. Before analysis and use, the copolymer was by dissolving in acetone, Precipitation cleaned in water in a mixer and drying in a vacuum oven. The characteristics are below mentioned in Table III. 4.3% by weight monoethyl ester of fumaric acid were present.

^H fi1 (? ") Production of ethyl acrylate / maleic acid

* anhydride copolymers

1) A 2 l resin flask was used as the reactor, the was provided with a stirrer, condenser and dropping funnel. A 710 ml batch of ethyl acetate and 0.2 g of benzoyl peroxide was added to the flask and refluxed under nitrogen with stirring. A mixture of 500 g of inhibitor-free ethyl acrylate, 10 g of maleic anhydride and 1 g of benzoyl peroxide was added to the dropping funnel. 50 ml of this monomer batch were all at once in the stirred and refluxed

placed heated solution in the flask. The rest was over | added over a period of 3.5 hours. After weitered Heating at reflux for 2 hours was the reaction-j mixture for removing solvent and remaining! Steam distillation monomers under one hood Subjected with good ventilation. The copolymer isolated in this way was mixed on a roller mixer Washed with water, partially dried on a heated rubber roll mixer, and then in a vacuum oven with nitrogen circulation 22 hours at 130 ° C heated to remove residual volatiles. Yield 448g.

2) The same apparatus as in the experiment Η, ^ ·> was used. The ethyl acrylate / maleic anhydride copolymer was prepared as follows: A mixture of 500 g of ethyl acrylate, 10 g of maleic anhydride and.

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25510U

0.5 g of benzoyl peroxide was added over a period of 4 hours to 490 g of ethyl acetate, which was 'heated to reflux.' After about 85% of this feed mixture had been introduced, 140 nil cyclo-; hexane and 35 ml of ethyl acetate was added After |.... the addition of the entire batch an additional 80 ml \ ethyl acetate were added followed by heating an additional 'hour at reflux the heat supply was turned off and the mixture stand 36 hours j then allowed to 0, 5 g of hydroquinone züge- \ sets, after which the copolymer by removing the i volatiles by steam distillation, was isolated in a well ventilated hood arrival.

i was finally on the roller mixer and in a vacuum j

oven dried (20 hours at 130 ° C). The yield
was 364 g.

The properties of the tests G, H, ^ * and
H, "v copolymers produced are below in
Table III named.

Table III

Copoly- Maleic Acid Inherent,, Wallace Acidity | merisate anhydride,% Viscosity Plasti- milliequiva-! city lent / g '■

G - 2.32 - 0.30 j

H ₍₁₎ 1.5 1.24 5 0.31

1.4 2.03 14 0.29

dl / g; measured at 30 ^° C. on a solution of 0.1 g
Copolymer in 100 ml of chloroform.

Acid-base titration with aqueous sodium hydroxide standard solution; the values "for H ,,., and H,«. were
0.15 milliequivalent / g each when using alcoholic potassium hydroxide solution. The proportion of
Maleic anhydride is derived from the sodium hydroxide

609821/0917

values calculated.

I. Preparation of an ethyl acrylate / butyl acrylate / MonO- "
ethyl fumarate terpolymer ___i____

As a reactor, a 'funnel with stirrer, condenser and drip-provided and held under nitrogen "used \ 2 1 resin flask. J

Monomeric ethyl acrylate and butyl acrylate were passed through aluminum oxide to remove polymerization inhibitors. Then 70 g of ethyl acrylate, 70 g of \

Butyl acrylate, 10.5 g monoethyl fumarate, 21 g nonylphen

Oxy-polyethylene glycol with about 15 units of the formula <-0-CH ₂ -CH ₂ - ("Igepal CO-730"), 1050 g of water and 1.0 g of ammonium persulfate are added to the resin flask and heated on the reflux condenser. A mixture of 113 g
Ethyl acrylate, 113 g of butyl acrylate, 9.4 g of monoethyl fumarate and 3.8 g of nonylphenoxy polyethylene glycol
"Igepal CO-730" gradually became one of these! Speed introduced that the reaction temperature * was kept at 89 to 93 ° C. After 1.4 hours! the entire batch was introduced and stirring was stopped
difficult. After a further 20 minutes, the temperature of the reaction mixture had risen to 96 ° C., whereupon
0.15 g of hydroquinone were added and the remaining monomers were removed by steam distillation in a well-ventilated hood for 2 hours.

The coagulated polymer was chopped into
washed in a mixer with water, twice in acetone
dissolved and reprecipitated in water in a mixer; dried with air, 3.5 hours at 72 ° C in one
Vacuum oven dried and finally dried on the roller mixer at about 130 ° C. The yield was
254g. The terpolymer formed was inherent
Viscosity of 1.51 dl / g (chloroform, 30 ° C) and one
Acid content of 0.24 milliequivalents / g (titration with
aqueous sodium hydroxide) or 0.23 milliequivalents / gj

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25510H

I (titration with alcoholic potassium hydroxide). The ter-j polymer contained 3.3% monoethyl fumarate. It became | Assuming that the rest of approximately equal parts j Ethyl acrylate and butyl acrylate consisted. i

J. EPDM / maleic anhydride adduct '

Maleic anhydride was based on an ethylene / propylene /; 1,4-hexadiene copolymer grafted. This copolyme- | Risat was a sulfur vulcanized elastomer j with a Mooney viscosity (ML-I + 4/121 ° C) of about 35 and contained the following monomer units: 61.4
Wt .-% ethylene, 32 wt .-% propylene and 6.6 wt .-%
1,4-hexadiene. It contained about 0.5 g-mole of ethylenic
unsaturated side chains per kg and had one
Wallace plasticity of about 28 to 100 ° C and one
Inherent viscosity of about 2.0 (measured at 30 C.
a solution of 0.1 g of copolymer in 100 ml of tetrachlorethylene). The copolymerization was carried out in solution in hexane in the presence of a Ziegler catalyst which
by mixing VCl. and diisobutylaluminium chloride
was made.

A Werner and Pfleiderer 53 mm twin screw extruder was end-side attaching 16 Zylinderab- \ cut of 1.27 cm diameter assembled. A short charging zone was followed by four reaction zones (zones 1 to 4), a vacuum connection zone (zone 5), a cooling zone (zone 6) and a nozzle zone. Provisions have been made for metering in the molten maleic anhydride at the front of Zone 1. Di «: snails consisted of kneading blocks, snails with
opposing pitch and screw conveyor, the so

were arranged to have one in zones 1 to 4

2
Pressure from 7.0 to 14.1 kg / cm and in zone 5 none

Generated pressure. The free volume of zones 1 to 5

corresponded to 0.91 kg polymer at the working temperature

o '

door. Zones 1 to 4 were at 300 C, zone 5 at

609821 / Q917

_ 4O -

26O ° C and zone 6, the cross-head and the nozzle preheated to 150 C.

The above-mentioned ethylene / propylene / 1,4-hexadiene copolymer was pulled into the extruder in the form of chips that passed through a sieve with a mesh size of 1.27 cm leads. The maleic anhydride was fed to the extruder in an average amount of 4.8% of the polymer weight metered in. The speed of rotation of the screw was 12 rpm and the vacuum port was turned on Vacuum of approximately 635 mm Hg is applied.

The content of maleic anhydride in the with a throughput of 2.79 kg / hour. extruded product 2.23% as determined by infrared spectroscopy and 2.19 % By weight, determined by titration in tetrahydrofuran with 0.1 molar tetrabutylammonium hydroxide in methanol. the Wallace plasticity of the product was 33 and the gel content less than about 5%.

After purifying a small sample by dissolving it in tetrahydrofuran and precipitating it with anhydrous acetone the content of maleic anhydride was 2.19% as determined by infrared spectroscopy and 2.05% by weight as determined by titration. The gel content was below about 5%. The inherent viscosity was 1.5 dl / g, measured on a Solution of 0.1 g adduct in 100 ml perchlorethylene at 30 ° C.

The remainder of the product was washed on a roller mixer for 20 minutes at 125 ° C and on a roller mixer dried from 15.2 χ 30.5 cm.

A number of other basic ethylene copolymers (experiments K through V in Table IV). Containing maleic anhydride as a comonomer was replaced by the above Copolymerization described prepared.

609821/0317

Table IV relationship
of the comonomers Melt index procedure Ethylene copolymer 73.4 / 20.1 / 1.5 12th K Ethylene / vinyl acetate /
Maleic anhydride Il 12th L. ti 73.3 / 24.6 / 1.6 26th M. It 96/4
37.7 / 12.3 '15
750 N
0 Ethylene / maleic acid
anhydride
It 74/24 / 1.3 220 P. Ethylene / vinyl acetate /
Maleic anhydride 10.8% maleic
acid anhydride 1700 Q Ethylene / 3-methylbutene /
Maleic anhydride 21% male
acid anhydride 2000 R. 11 71/20 / 3.5 920 S. Ethylene / vinyl acetate /
Maleic anhydride 33/12 750 T Ethylene / maleic anhydride 60/33 / 1.7 220 U Ethylene / vinyl acetate /
Maleic anhydride 62/33 / 4.3 290 ν - Il

Production of side chain polymers (with terminal amino groups) j

Procedure AA

A heavy glass tube was used to make a low molecular weight one Polymer used. In the tube I 50 g of caprolactam, 10 ml of n-hexylamine and 0.25 ml of water were ι given. The tube was purged with nitrogen and under!

ο i vacuum sealed. It was 15.5 hours at 220 C j

keep.

The polymer was removed from the tube and used to remove residual unreacted caprolactam and Amine washed with hot water and dried. The polymer had a melting point of 165.degree by differential thermal analysis (DTA). Analysis for end groups showed 940 milliequivalents / kg NHp. the end a molecular weight of about 1,050 was calculated from these results.

Method BB

In the same manner as in Method AA, a polyamide was made from 50 g of caprolactam and 12.5 ml of n-hexylamine manufactured. The tube was heated to 255 ° C for 20 hours. The polyamide had a melting point of 177 ° C.

Procedure CC to GG

A heavy stainless steel pipe was used to make low molecular weight polyamides. N-Hexylamine was used as a chain initiator in the amounts given in Table V. Solid, normal caprolactam, which had been cleaned in the usual manner was used. This caprolactam probably contained water in Trace amounts. Otherwise the water was excluded from the reaction mixture for initiation by water and subsequent chain termination by carboxyl groups. The tube was evacuated and for prevention

£ 09821/091 7

flushed with nitrogen by oxidation reactions, then filled with nitrogen again, sealed and heated, j The tube was agitated during the reaction time. In all tests, the tube was open during this time Heated to 255 ° C.

The products were analyzed for melting point and end groups. The analysis of the end groups showed that only about! 0.2% of the molecules had terminal carboxyl groups.

S09821 / 0917

Tabel

CD to OO

O CD

procedure Capro -
lactam
G H ₂ O
ml N-hexyl
amine
ml Temp.
⁰ C Time
Hours. Enamel
Point
according to DTA
⁰ C Milliequivalent / kg
NH ₂ COOH 1.7. Molecu
lar
weight CC 50 0 9 255 16 1Ö7 943 2.6 1050 DD 50 I. 0 10.5 255 16 193 Ö71 1.7 1140 EE 50 0 11.5 255 16 196 Ö77 1.3 .1130 FF 50 0 10.5 ■ 255 16 193 1171 1.6 347 GG ' 150 0 31.5 255 16 191 1027 960

• fs-4s-

(Jl

Traversing HH to OO

Ifi in the same way as for procedures CC to GG The polyamides listed in Table VI were paid for manufactured. The reaction was carried out at 255 ° C for about 16 hours.

B09821 / 091 7

Table VI

σ?
ο
co

procedure

HH

JJ
KK
LL

MM
NN
00

Lactam

Amine

Melting point, DTA, ^Q G

Milliequivalent / kg

NH.

COOH

Molecular ;weight

50g. Caprolactam

50g. Laurolactam

47 x 5g caprolactam 2.5g laurolactam

45g caprolactam 5g.L aurolactam

A-Og. caprolactam 10g. Laurolactam

8Og. caprolactam 25g laurolactam

70g. caprolactam 30g. Laurolactam

20 g. Stearylamine

5 g. butyl

amine

10.5 ml n-H exylamine

dd

12 ml. N-Hexylamine

4 ml. N-H.exylamine

204 204 200

189

177 ISO 173

934

492

1169 1113 1103 720 345

not verifiable r 1052

$ 120

not detectable 1.6

a.o

S4.7

903

1390

255IQ-U

Procedure PP to XX

Polyamides with terminal amino groups were after the! Process PP to XX produced, the details of which are given in full in Table VII. Further details are given for the QQ _; SS, VV and XX ge j

which are common practice. |

Procedure QQ j

■

In each of two 400 ml stainless steel shake bombs the steel was a mixture of 120 g of caprolactam, 10 g of stearylamine, 0.3 g of diethyl phosphate and 120 ml of benzene given. Both bombs were flushed with nitrogen, sealed under nitrogen and at 275 ° C for 17 hours shaken. The granular product cakes moistened with benzene were combined and placed in acetone for 5 days and then extracted with acetone overnight in a Soxhlet apparatus. The powdery obtained Amino terminated nylon product was air dried under the hood and then one hour dried in a vacuum oven at 50 ° C. The analy- values are given in Table VII.

Procedure SS

A batch of 300 g of caprolactam and 100 ml of water was sealed under nitrogen in a 1.4 l stainless steel vibrating bomb and heated to 280 ° C. within 2.1 hours, kept at this temperature for 3 hours and then cooled to room temperature. After a further 650 ml of water had been added under nitrogen, the bomb was sealed again and shaken while it was allowed to pass through the following temperatures: heating to 210 ° C. in 1.2 hours; 15 minutes at 210 ^° C .; Cooling to 135 ° C in 20 minutes; 2 hours at 135 ° C. and subsequent cooling to room temperature within 1.2 hours. The product obtained, a partial slurry of powder, granules and cake,

609821/0917

2551QH

was partially dehydrated by filtration and then crushed in a mixer with fresh warm water. By adding acetone, the volume of the j

Slurry increased by 50%. The solids were filtered off. By drying in air under a hood and then drying in a vacuum J

ο ι

Heating cabinet for 8 hours at 100 C (nitrogen circulation) 217 g of amino-terminated nylon product were obtained. The analysis values are in Table VII called.

Procedure VV

A batch of 769 g of caprolactam, 32 g of butylamine and 15 g of water was sealed under nitrogen in a 1.4 liter stainless steel shake bomb. The bomb was heated to 280 ° C. over 2.5 hours, shaken at 280 ° C. for 7 hours and then cooled to room temperature within 3.2 hours. The product, a crumbly cake, became mechanical crushed to a coarse-grained state. A portion of 317.9 g of the total product was overnight in rolled a 7.6 l vessel with 1.42 l of methanol. Insoluble material was filtered off, in two portions washed with 0.47 l of methanol, dried briefly in the air and then in a vacuum oven with Nitrogen circulation dried at 75 ° C. for 3 hours. The dry extracted product weighed 267.6 g. The analytical values of a smaller sample (15 g) contained in the extracted with methanol in the same manner are given in Table VII.

Procedure XX

A mixture of 70 g caprolactam, 6 g 1-octadecylamine and 195 ml of diphenyl ether was placed in a 0.4-1 shake bomb made of stainless steel. After the system is evacuated twice and filled with nitrogen

609821/0917

-49-25510H

it was sealed under vacuum and about
Shaken for 8 hours at 260 ° C. Heating and shaking continued for two days. The final temperature

was 235 ° C. j

The resulting mixture was washed on a filter with acetone \ and to remove diphenyl ether three days
shaken in acetone. The product was on a filter; collected, washed with acetone and stored overnight in a! Soxhlet apparatus extracted with acetone. By drying | in air and then in a vacuum desiccator at 50 C j

the nylon-6 was made as a powder with an inherent viscosity! of 0.21 dl / g (at 30 ° C in m-cresol) and 0.383, 0.388
Equivalents —NH “groups / kg obtained (corresponding to a] molecular weight of about 2600 and a degree of polymerization of about 21).

09821/0917

a b e 1 1 e VII

Production of low molecular weight nylon-β with PP 19-5 QQ KR SS ¹ settle Uli Amino groups .5 7 ' W. XX 70
"6 I. Polymerization under
Nitrogen,
Composition of
Approach, g _v IT W. vj! Caprolactam
Stearylamine 1U0
10 20th 295 300 65Ö - " 283 769 ^; O
I. Octylamine 23 283 20.8 769 . Butvlamin lu
280, 210 32.2 32 _ CD . C-aminocaproic acid 5 3, 0.3 32 15th (JO
to water 100 g s m Diethyl phosphate 0.2 Ö.6 U 15 ' . ^ cn Diphehyl ether 135 ngST_a O benzene 2U0 O CD Thinner, according to
Polymerization, g \ ^a ) -J benzene 300 water oU
260, 235 Methanol U51 lU
2U5 56 Polymerization conditions
Size of the swing tube
Hastelloy or not- ₀ ^
rusting steel, J ₁ I ter * ._.
Reaction ^{temperature, 0} C ^ ' 260 2 χ OU
275 1
2U5, 230 U51 3 Diluent
middle Response time, hours' ^D ^ 17th 20, 0.5 iU
280, 230 lU lU
280, 230 28Ο ■ - Schnitzel Granulating process ^ ' e r d ü η η u η 3.5, 0.5 3.5, O i t t e 1 -

Tabel

VII (cont.)

Manufacture of low molecular weight nylon-6 with terminal amino groups Cleaning process

Soxhlet extraction overnight, solvent reflux overnight in 10 times the solenoid weight

it extract, on tfalzenmi- * p sher overnight, "" solvent

W washing in the mixer, ■ "* solvent 3 centrifuging / decanting " J2 ren, .vaschen, solvent.

- * (repetitions)

"^ Drying in the air after filtering off: Drying in a vacuum oven (N ₂ discharge): Temp./time ( ⁰ C /, hours)

Properties of the purified nylon-6

Yield, g / \

NHp end groups, nuiqu./g COÖH end groups, "(d) yj.inh. (M-cresol, 30 ⁰ C) ifeC melting point, ⁰ C (e) molecular weight, from NH ₂ degree of polymerization

F?

Acetone acetone

RR

TT

UU

water

(β)

50 / I 100/10 100/8

(H)

100/15

acetone

Methanol

Methanol (3)

100/2 * »·

75/3

101.5 ~ 18O ~ 253 217 250 • 5 222.2 • ■ ^ 652 798.3.,. 'O.383' CP 0.198 0.2Ul O.U28 ΟΛ5 O.6I 0.U6 —0.U6 / Dd O.287 .5 0.21 'VJ f 0.38 O.36 0.27 O.30 O.I9 0.23 "-Ό.29 / * ~ Λ 216 217 210 220 ' 209 21U ~ 217 26OO V_J 5050 U15O 2336 2220 2170 2170 2020 21 U2.U 3U.5 I9.5 I9.5 13th 18th I8.5 17th

Footnotes to Table VII

a) With the help of the inert diluent, the nylon was obtained in finely divided form, if the polymer shaken with the diluent at a temperature above the melting point of the nylon became.

b) The table does not indicate the times that were required to reach the reaction temperature (generally 1.3 to 2.3 hours) or for cooling (about 1 to 3 hours). A second pair of Temperature and time values refer to a second heating period after adding the diluent after the Polymerization.

c) A nylon sample of approximately 0.8 g is made by heating dissolved in 25 ml of o-cresol and with 1.5 ml of water and. then treated with 7.5 ml of chloroform, cooled and potentiometric with ethanolic O, 3n-Kaliumhydroxycjl titrated (Beckmann combination electrode 39501).

d) A nylon sample of about 0.1 g is prepared by heating in 80 ml of m-cresol dissolved. After cooling, 10 ml of chloroform are added. The mixture obtained is with 0.01 n-2,4-dinitrobenzenesulfonic acid in acetic acid titrated potentiometrically (glass-modified calomel electrode) .

e) Samples were taken at a rate of -10 ° C / min. by a temperature cycle of 50 ° C - ^ - C- ^ 250 ^{0 0} 50 C - out> 25O C, and the maximum melting energy value of the second heating cycle was used as a melting point genommei Usually a shoulder was observed at a lower temperature.

f) Caprolactam, residual amine as initiator and never- ' their oligomers were not extracted before analysis.

609821/0917

2551QH

g) Solvent for washing in the mixer during the experiment | SS: (1) hot water, (2) acetone / H ₂ 0 (1/3). j

h) Solvent for washing in the mixer in the experiment j TT: (1) methanol, (2) methanol / acetone (5/2).

Procedure YY to KKK procedure YY

Caprolactam / n-hexylamine oligomers

In a 200 ml pressure reactor 50 g (0.442 mol) of j έ-caprolactam (CL), 10 g (0.099 mol) n-hexylamine (HA) and) 0.2. added g (0.011 mol) of water. The reactor was cooled in a dry ice-acetone bath, twice with nitrogen flushed under vacuum, evacuated and kept at 250 ° C. for 16 hours, while the contents under the autogenous pressure was standing. The cooled product was a soft white solid. A 45 g portion was centrifuged first extracted with about 900 ml of acetone-water (1: 1) and then with acetone. The air-dried residue weighed 25.5 g and was easily crushed to a fine powder. The analysis showed 865 equivalents terminal Amino groups per 10 g corresponding to a degree of polymerisation (DP) of about 9. With the differential scanning calorimeter (DSC) an upper endothermic melt energy value was determined at 196 to 198 ° C.

Additional samples of CL / alkylamine oligomers were obtained following the procedure described above, but without the use of water manufactured. Reactors up to 1300 ml in size were used as required. The values for this Products are listed in Table VIII below.

609821/0917

Table VIII

procedure CL
G Amine
G 5 The end- ,
ν 9
prey
G ι) ^DSC ~
Schmel
Point, End group
z- (equ. / 10 ⁶
C NH ₂ CO η
G)
₂ H .8th Polymeri
degree of sation
(approximately) zz < ^b > 50 HA, 20th 20.3 205 710 54 .84 12! AAA 100 HA, 2.5 83.2 184 1162 5 - 7th BBB 50 HA, 20th 31.0 207-8 590 8th .6
.2 15 " O CCC iod EA, H VJl
VJl 78.0 - (1160) 7th OD
ro DDD
EEE VJl VJl
O O HA,
HA, 20th 38.0
27.0 - 785
442 27
10 .4 10
20th ο FFF 100 HA, 29 71.2 - (1160) - .3 7th GGG 100 HA, 120 47.0 177 1322 0 - 5.8 HHH 600 KA, 53 529.5 - II89 4th 6.5 III 50 HA, ^e%; , 29 24.3 < ^d 2285 3 YYY 200 BA ^ 171 1237 6.5

KKK 100 ODA * · ', 54 108-1076-5.8

(a) All experiments were performed with acetone as the primary extraction solvent.

(b) The reaction mixture also contained 50 ml of benzene and 0.2 g of diethyl phosphate. the Reaction was carried out at 275 ° C.

(c) BA = n-butylamine; ODA = n-octadecylamine.

(d) Extracted with petroleum ether, benzene and diethyl ether.

25510U

Process LLL to NNN Laurolactam / n-Hexylamine oligomers

In the same manner as in the method YY but at a temperature of 300 ° C., laurolactam / n-hexylamine oligomers became (LL / HA) made from laurolactam (cyclic lactam from 12-aminolauric acid) and n-hexylamine. the Results are given in Table IX below.

609821/0917

Table IX

LL ^(a)
G Laurolactam / n-hexyl yield
G amine oligomers End group
(Equ. / ICT
NH ₂ 2n
³ g)
CO ₂ H Polymerisa
degree of movement
(approximately) procedure 100 HA
G 48.5 DSC
Melting
point, C ■ 1335 - 3.3 LLl / ^d > 50 50 (C)
35.5 _ 733 - 6.5 MMM • 50, 7th 31.8 ° 162 657 7.2 NNN 5. 164 .5 , 0

(a) All experiments with 0.4% water, based on laurolactam.

(b) Acetone was used as the primary extraction solvent.

(c) methanol was used as the primary extraction solvent,

(d) Carried out in a 400 ml reactor.

■ ro cn • cn

CD

Procedure OQO to PPP

Manufacture of 12-nylon with terminal NH "groups

Procedure OQO

A mixture of 59.6 g of Ctf-laurolactam and 4.8 g of 1-octadecylamine was heated in a glass polymerization tube. After the melt formed had crystallized, 0.16 g of diethyl phosphate (CH ₃ CH ₂ O) ₂ PO ₂ H were added. The tube was then evacuated and filled with nitrogen about five times. The neck of the tube was closed under vacuum. The mixture was then held at about 285-288 ° C for about 9.5 hours. The 12-nylon obtained (yield about 45 g) had a melting point of about 145 to 150 ⁰ C, an inherent viscosity of 0.34 (at 30 ° C in m-cresol) and 0.225, 0.226 equivalents -NH ₂ groups / kg | (corresponding to a molecular weight of 4430 and a degree of polymerization of about 21). i

Process PPP!

A mixture of 50 g of cü-laurolactam and 10.5 ml (13.8 g) n-Hexylamine was placed in a heavy stainless steel tube. The tube was evacuated with nitrogen purged, filled with nitrogen and then sealed and held at 255 ° C. for 16 hours. The obtained nylon contained 0.492 equivalents NHg groups / kg. The nylon had thus a molecular weight of about 2030 and a degree of polymerization of about 9.5.

More nylon 12 products

Additional samples of nylon-12 were made by the PPP method using n-hexylamine as a polymerization initiator. The products had degrees of polymerization of 5.3, 7.0, 10.2, 14.3, 15.6, 24.0 and 15.6.

609821/0917

Examples 1 to 13

The properties of those prepared according to the following examples Products were determined according to the methods described below.

The notched Izod impact strength (Izod) was determined by the method ASTM D 256-73 determined. Test specimens are placed in a laboratory press at 190 ° C. in the form of plates Size of 76mm 76mm 3.18mm pressed. Test rods 63.5 mm by 12.7 mm in size are cut from the plate and scored as described in ASTM D 256-73. The test specimens are kept at room temperature for 16 to 24 hours after cutting and scoring and before testing conditioned. 5 bars are tested from each sample. The average value is called the notched Izod impact strength given in cmkg / cm notch.

The impact strength was determined using the ball drop test determined from different heights as follows: Plates 0.76 to 1.02 mm thick were placed in a press pressed at 190 ° C. The panels are kept at room temperature for 16 to 24 hours prior to testing. The test is made with a Gardner Impact Tester, Model IG-1120M. The tester is weighing 3.63 kg with a ball 12.7 mm in diameter provided at the end. The weight is placed on the sample, which is placed on a metal sheet with a hole 16.3 mm in diameter immediately below the point of impact of the weight is dropped. The weight falls through a pipe marked in cmkg. The point at which that Weight is released is recorded as impact energy for this case. The force at which 50% of the specimens break is given as Gardner impact strength in cmkg. The thickness of the samples can be measured and the values obtained can be expressed as impact strength in cmkg / mm can be specified.

609821/0917

.59-25510H

The vapor pressure osmometry was carried out according to a standard method determined by R.U.Bonnar, M.Dimbat and F.H. Stross; "Number-Average Molecular Weights", Interscience, New York 1958, is described. It is about a ; Solution method. The solvent must dissolve the material to be tested well. The solvent used was o-dichloro benzene preferred. The test was carried out at 100 ° C. by-i

guided.

The flexural modulus was determined using the ASTM D-790-71 or a modification of this method. The test specimens are shaped at 190 C in a laboratory press pressed from rods with a size of 127 mm 12.7 mm 3.18 mm (or in foils with a size of 50.8 mm χ 12.7 mm). The rods (foils) are kept at room temperature for 16 to 24 hours before the test. The test will with a measuring length of 50.8 mm (or 25.4 mm) at a speed of the pulling clamp of 1.27 mm / minute (or 5.1 mm / minute) carried out. The flexural modulus (tangent modulus of elasticity) is determined with the help of the ASTM is calculated. The value obtained will be

ρ is expressed as the flexural modulus in kg / cm.

The dimensional stability under heat under load was determined as follows: The test specimens were ^{pressed in a laboratory press at 190 °} C. in the form of rods with a size of 127 mm × 12.7 × 3.18 mm. These bars are tested according to the ASTM D 648 method. The bars are held at room temperature for 16 to 24 hours prior to testing. Weights are placed on the loading bar

ρ is placed until the fiber stress is 18.56 kg / cm. The rods are heated in a bath until one Deflection of 0.25 mm is measured. The temperature at which the rod is bent by 0.25 mm is expressed as the diameter

2 bending temperature at a fiber tension of 18.56 kg / cm

specified.

B09821 / 0917

Production of graft copolymers

In Table X are the details of manufacture, composition, and properties of representative ones Graft copolymers indicated according to the invention.

For all graft products, plates could be used for the tests by briefly pressing at 235 C followed by rapid cooling (about 2 minutes) and immediately Demould be produced. By tempering these plates for 4 to 5 hours at 135 C, the Compression set generally improved by about 20 to 35 points, but that had Annealing has little effect on other properties. That Grafting procedures used in Example 7 in Table X illustrates the procedure:

A mixture of 36 g ethylene / vinyl acetate / maleic anhydride base copolymer, prepared according to Method C, 14 g of powdery low molecular weight Nylon-6 containing terminal H “N groups and prepared according to method SS, 0.1 g of tris (mono- and -dinonylphenyl) phosphite as a stabilizer ("Polygard", manufacturer Uniroyal), 0.1 g N-phenyl-N · - (p-toluenesulfonyl) -p-phenylenediamine as stabilizer ("Aranox", manufacturer Uniroyal), 0.1 g 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-buty1 -4-hydroxybenzy1) benzene ("Ionol 330", manufacturer Shell) and 0.05 g of a mixture of potassium iodide and cuprous iodide (weight ratio 7: 1) was on an unheated rubber roller mixer homogenized as well as possible. The resulting mixture was then placed on an electrically heated roll mixer which was held at 215 ° C, and partially blanketed with nitrogen at 215 ° C for 15 minutes kneaded to effect the grafting. The material was then ready for processing.

609821/0917

_ .Tabel example 1 2 X ₄ (a) Graft copolymers 6th 7th I. cn
cn Manufacture, composition and Basic polymer E.
branched
alternating
E / feA / AA / MAnh ^P (4)
mixture
branched
aging.
E / jiA / MAnh as in
example
1 5 ^H (D
as in
example
5 C.
E / VAc /
MAnh l Profpfstelle on
Basic copolymer MAnh as in
Example 1 properties of as in
Example 1 ^H (2)
EA / M appendix as in
Example 1 as in
Example 1 Concentrate the plug
places, milliequiv. / g 0.235 0.215 3 0.18 as in
Example I. 0.155 0.245 Side chain polymer üü VV ^D (4)
as in
example
2 PP 0.15 SS TT ο
CD
OO initiator Octylamine Butylamine as in
Example 1 Stearyl
NH ₂ 44 ^H 2 ° as in
Example 1 ro NH concentration, mAquiv./g 0.46 about 0.46 0.35 0.198 as in
Example 4 0.45 0.61 ο
/ ο Nylon, parts / 100
Parts of resin ( ^e > 50.6 40 WW 80 0.24 30th 39 Apparatus for
Graft reaction Extruder Plastograph
(f) " as in
Example 2 Plasto-
graph 55 .falzen- _(}
mixer iValzen-
mixer Conditions of
Graft reaction: approx 0.495 Plasto-
graph Temperature of, *
lieaktorwand, ⁰ C approx. 230 220 50 about 210 ^ 220 215 Dwell time, minutes about 16.4 10 Plasto-
graph 20th about 210 ⁽ⁱ⁾ 15th 15th 20th 220 10

Table X (cont.)

example

11

13th

Basic polymer

Profpfstelle on base copolymer

Concentration of the grafts, milliequiv. / G

Side chain polymer initiator '

NH "conc., MEq. / G

Nylon, "parts / 100 parts resin ( ^e '

Apparatus for grafting reaction

Conditions of the grafting reaction;

Temperature of the reactor wall, ⁰ C ¹ '

Dwell time, minutes

as in E / MA / as in EA / FAME ΕΛ / ΒΑ / as in ßisp. 7th '■ NhME ßisp. 9 FAME Example 12 as in ) '. «ΆΜΕ as in FAME as in as in Example 1 Example 9 Example 11 ice cream 11 0.173 0.25 0.25 0.29 0.24 0.24 MR TT TT TT TT TT as in as in as in as in as in as in Example 1 Example 1 ßisp.1 Example I. Example 1 Example 1 0.428 0.61 0.61 0.61 0.61 0.61 34 40 39 50 39 39 Plasto- Extruder Iv'alzen- Whale Rollers Plasto- graph mixer mixer mixer graph

about 230
about 6.7

215

15th

210 12

220 10

Table X (cont.)

Production of graft copolymers, composition and properties

Example 1 2 3 k _yy_ _6_ 7 8 9 10 11 12 13

ο, graft copolymer,

ο physical properties

co Shore A hardness '83 76 8l 85 77 6 ^ 91 85 67 63 .92 83 71

Zt tensile strength, kg / cm ² 22lf 220 I65 189 159 120 167 I62 lln 13 ¹ * 139 97 87.9 '

O ■ 0Λ

cd elongation at break, % 370 1 + 60 ^ 30 300 220 270 390 330 l * 8o 500 180 210 2to ^<oJ

^ lQO ^ module, kg / cm ^ 85.8 67 58 110 79 · ^ 58 78Λ 8k k3 28 115 70 3k

Compression set
(22 hrs / 70 ° C, method B),
% 23 22 35 33 26 35 32 3 ¹ + 28 3 ¹ ^ 37 38 ^ 3

to απ σ

25510H

Footnotes for Table X

a) A small amount of aniline (0.4 parts per 100 parts resin) was added after the grafting reaction.

b) E = ethylene; EA = ethyl acrylate; (alt.) denotes an alternating as opposed to a random copolymers; VAc = vinyl acetate; MA = methyl acrylate; BA = butyl acrylate; AA = allyl acrylate; MAnh = maleic anhydride; ΜΑΜΕ = monomethyl maleate; FAME = monoethyl fumarate. These units are polymerized into the basic copolymer.

c) The mixtures prepared on the roller mixer were immediately before the grafting reaction in a 130 ° C held vacuum oven with nitrogen discharge. The later experiments showed that this treatment only has an insignificant influence on the physical properties of the products would have.

d) The alkyl radical of the initiator becomes one of the end groups of almost all polymer chains. The other end group is almost always NHp.

e) Amount of nylon in parts by weight per 100 parts by weight of base copolymer.

f) Brabender-Plastograph, an apparatus with a small, electrically heated chamber with two spiral-shaped Rotary bodies, which the polymer at a selected high temperature under the action of shear forces able to mix and knead.

g) An electrically heated roller mixer was used for the required temperature.

h) The polymer is not necessarily always at this temperature. Usually there is one first Preheating period before, after which the temperature may be

609821/0917

.es- 25510H

slightly exceeds the value mentioned i due to an exothermic reaction. j

i) Exact temperature values were not determined here. j

j) All graft products contained, except for those here j components called a mixture of stabilizers, j

which was very similar to the mixture j mentioned in detailed example 7. j

The following ASTM methods were used: Shore A: D-2240-68; Tensile Strength (T): D-412-68; Stretching: (E _ß )! D-412-68; Module at 100% elongation (M _-100 ): D-412-68. ;

IUU ι

All values were measured at 25 ° C. Deformation resti after compression after 22 hours at 70 C: D-395-67. The test specimens were stored for 4 hours at 135 ° C annealed.

Examples 14-22

Production of further graft copolymers of nylon-6

and nylon-12 based on ethylene / methyl acrylate / mono-

ethyl maleate copolymers

Copolymers of ethylene, maleic anhydride (MA) and monoethyl maleate (MAME) were made as described above Process A prepared, but the quantitative ratio of the comonomers was changed. Low molecular weight j Nylon-6 and nylon-12 were either on a roll mixer under nitrogen at about 225 ° C or in one Twin screw extruder grafted on at about 225 ° C. the Details of the preparation and the properties of the products are given in Table XI below.

To determine the tensile strength and flexural strength test specimens were produced by injection molding at 225 to 235 C and kept at 23 C for at least one day. The following test methods were used:

Tensile strength and elongation at break were determined according to ASTM D-638-72] the flexural modulus is determined in accordance with ASTM D-790-71. The torsional

609821/0917

25510H

Modulus values were measured by the method described in j "Anelastic and Dielectric Effects In Polymeric Solids" by N.G. McCrum, B.E. Read and G.Williams, pp. 192 to | 195, John Wiley and Sons, Inc., New York 1967, is described. The melt index was determined by the method; ASTM D-1238-73, Condition E or Condition A, determined, j whereupon it was converted into an equivalent value for Condition E. j

609821/0917

Tabel

XI

example Xt Equivalent ratio 25th t 15S, 165 12.66 χ a W. Xb rf ' λ χ / ■ ί 19th XO U Xb / υ ίΧ U * i • I. .69 -Base polymer 1/2 UAME / NH 220, 231 9.30 π Ct, β 1 84. H 40.6 . £ 6 % Ethylene 36.3 DTA melting point, ° C 2.23 552 7.41 36.3 40.6 40.6 65 42.8 42.8 42.8 42.8 50.8 .20 % Methyl acrylate 39.7 maximum ² 61 1.57 39.7 50.8 50.8 20th 51.4 51.4 ■ 51.4 51.4 8.6- ' * \ 22nd . % V [AME 24 Final melting point ^! 190 Ό.90 24 8.64 8.64 16 5.76 5.76 5.75 5.76 6.6 , 3.) ! l8 Melt index I 32.8 Flexural modulus, kg / cm Pyn / cm 0.23 32.8 6.6 6.6 11 4.5 4.5 4.5 4.5 12th . 12 ^ t ^ nylon Tensile strength, kg / cm O.09 6th 6th 6th 05 6th 6th 12th S. F ⁵ A ³ .CB ΟΙ Degree of polymerization 6th Elongation at break,% " 0.04 7.0, 10.2 14.3 04 24.0 24.0 15.6 39.5 .02 cn End group ⁷ * ° ( Torsion modulus xlO, Η.ΑΛ ' COOH COOH COOH COOH HA ^<a> COOH 25th
Ά _ο % Polyamide
Ij ^ h ^ h ty * 4 * ^ * ^ vt i ^ 4 * ^ i "Il i λ · λ « -18O ⁰ C 35 25th
η 1 33 25th 3 5 25th 40 Q 6 ■ ο KeaKLion type -10O ⁰ C. ' α X η. πι S C UAOi 41 1.04 CD -5C ⁰ C. 1.38 .77 1.05 90 1.00 1.63 54 1.02 1.90, 1.34 59 OO
ISJ 0 ⁰ C. .94 18th 07 54 r 2D ⁰ C. .42 76 42 00 -Γ5 8 ■ - »% 5C ⁰ C. 180 .13 207 07 209 214 18th 212 158 203 89 153 CD ioo ° c. ■ 195 .64 213 05 213 219 16 219 175 . 217 55 510 15O ⁰ C. 10Ö3 .50 91 04 178 132 12th 23 30th 1019 20th 95 -J 92 .20 68 02 62 61 06 25th kk 145 12th ■ 190 130 .11 400 015 230 120 04 3 00 520 310 14th 14th 14th 16. 15th 15.29 27.59 14th 8th 11 ■ ίο. 11. 11. 9.23 16.97 9. 6th 8th 4th • ε. 5. 5.60 9.39 S. 2 . 05 .10 1. 0 1 0. 0. 0. Ο.04 0.10 • ο. O 0 ο. O. 0. Ο.03 O.03 0. 0 O 0. O. 0. 0.Ol O. 04 0. •. ο 0 O. ο. 0. - - 0.

(a) N-hexylamido group, -C-NH-

cn ■ si

25.51QU

Examples 23 and 24

Production of graft copolymers with nylon-6 and nylon-12 on EPDM copolymers

A Brabender Plastograph was used which has a capacity of about 50 g and heated by circulating oil (temperature 250 ° C). The material was kneaded by means of cam-shaped paddles under shear action The sample was kept under nitrogen for the entire duration of the experiment.

After adding 30 g of the above-described adduct J of EPDM copolymer and maleic anhydride were an antioxidant mixture, an oil mixture and nylon-6 or Nylon-12 with terminal amino groups (products XX or 000) added one after the other as quickly as possible. Then became mixed for another 12 minutes. The nylon graft copolymer obtained it was delivered. The characteristics of the products with grafted nylon-6 and nylon-12 are listed in Table XII below.

The Antioxydansgemisch used (0.7 g) consisted of 0.3 g of N-phenyl-N '- (p-toluenesulfonyl) -p-phenylenediamine ( "Aranox"), 0.3 g of 1, 3, 5-t _r imethyl -2,4,6-tris (3, 5-di-tert-i-butyl-4-hydroxybenzyl) benzene (Ethyl Antioxidant 330, formerly "Ionox 330") and 0.1 g of a mixture of potassium iodide and copper (I. ) iodide (weight ratio 7: 1).

The oil mixture consisted of the antioxidant tris (mono- and -dinonylphenyl) phosphite ("Polygard", manufacturer Uniroyal) and the paraffinic oil "Sunpar" 2280 (ASTM D-2226, Type 104B, Saybolt Universal Viscosity values 2907 seconds and 165 seconds at 37.8 ° C or 98.9 ° C; specific gravity 0.8916 at 15.6 ° C; density 0.8879 g / cm ³ ; molecular weight 720; viscosity-gravity constant 0.796;

20 refractive index n _ß 1.4908). All mixtures contained

0.3 g of antioxidant. The amount of oil was 10.5 g for the graft copolymer with nylon-6 and 8.5 g for the graft copolymer with nylon-12.

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Table XII

Tensile strength, kg / cm

Elongation at break,% 2 modulus in kg / cm

100% elongation 200% elongation 300% elongation Deformation rest at break,% Deformation residue after

Compression

(Method B, 22 hours / 70 ° C),% Shore A hardness

Tear resistance at high tear speed, 127 cm / min., Kg / cm

Graft copolymer with

Nylon-6 Nylon-12; 97.7 79.4 66.1 680 620 660 26.7 33.7 36.6 40.1 47.1 46.4 40 80
i 77 83 66 84!

11.8

21.4

Example 25

The ethylene copolymer produced according to process K and the polyamide j produced according to process AA were dissolved in hot hexamethylphosphoramide. The j solutions of the polymers were in a ratio of j 5 parts of ethylene copolymer mixed with 1 part of polyamide. This solution was kept hot for about 5 minutes and then j poured into cold acetonitrile, which was stirred rapidly, to precipitate the polymer. The polymer was filtered off, washed with acetone to remove excess solvent and dried.

A film was produced by pressing at 185.degree. The infrared spectrum showed almost complete conversion of the anhydride group, a sign that the short Polyamide chains had been attached as side chains to the longer chain of the ethylene copolymer.

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- γο -

Example 26

20 g ethylene copolymer (method L) and 4 g polyamide! (Procedure BB) were mixed on an electrically heated to 175 C \ two-roll mixer for 5 minutes. The infrared spectrum of the reaction product obtained allowed! Recognize almost complete conversion of the anhydride groups ¹ .

Examples 27 and 28 In the manner described in Example 25, the

polyamides produced according to processes HH and II j with the ethylene copoly- | produced according to process M merisat implemented as solutions in benzyl alcohol. The j infrared spectrum showed that more than 50% of the anhydride j groups reacted.

Example 29

30 g of polyethylene which had been modified by copolymerization with K% maleic anhydride (method N) were mixed on a two-roll mixer at 200 ° C. with 12 g of polyamide (method GG). The sample was pressed into a clear film at 230.degree. The infrared spectrum showed that more than 80% of the anhydride groups had reacted.

Examples 30 to 36

In the manner described in Examples 25 and 26, a number of graft copolymers were under Using the ingredients listed in Table XIII. In the case of Example 32, a melting point became measured at 189 C (differential thermal analysis = DTA).

Examples 37 “38 and 39

Three graft copolymer resins were made by implementing d_es melted resin on a two-roll mixer at 200 C for 2 minutes to the

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play described way manufactured. The strength j

properties of the graft copolymers are

Table XIV compared to the values for those not

called grafted ethylene copolymers. You let!

recognize the greatly increased tensile strength that j

Ethylene copolymers due to the presence of the poly;

amide side chains. i

Table le XIII GG !
Mixing process ι at
game
No. Ethylene
Copolymer
(Procedure) MM Roller mixer
200OC 30th 26 g 0 polyamide
(Procedure) NN
NN dto. 31 40 g P 13 g NN Roller mixer
180 ° C 32
33 40 g P
26 g Q 8 ε 00 Solution in hexa-
methylphosphorus
amide 34 6 g R. 8 g
13 g GG Roller mixer
190 ⁰ C 35 25 g N 3 g Roller mixer
200 ° C 36 26 g V 10 g 13 g

809821/091 7

255Ί0Η

Example of ethylene copolymer
No. (procedure)

Table XIV

Caprolactam tensile strength elongation polymeric kg / cm ^% (process)

37

GG

38

GG

39

GG

101.6 555 27.8 (ver
equiv
drive T) 1400 231.3 475 111.1 (ver
equiv
drive M) 400 141.7 530 82.3 (ver
equiv
drive 0) 700

Examples 40 and 41

The value of the graft copolymers described above in adhesives becomes evident when the adhesive has resistance to loosening of the adhesive bond is checked at elevated temperatures. The following is the use of the according to Examples 33 and Pforpfmischpolmerisate produced in a hydrogenated Rosin ester ("Foral 105", manufacturer Hercules) is described.

The adhesive according to Example 40 consists of one on the two-roll mixer at 185 ° C, the 65% of the hydrogenated rosin ester (Foral 105) and 35% of the graft copolymer prepared according to Example 33 contains. This mixture was made up using a hot plate and a Meyer rod Kraft paper applied. This coated paper was then onto a second uncoated Kraft paper by pressing for 3 seconds at 200 ° C under one

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2
Pressure of 0.7 kg / cm laminated. The laminate was cut into strips 12.7 mm wide to determine the tear strength. A 50 g weight was used in an attempt to pull the strips apart.

The adhesive according to Example 41 consists of a similar mixture based on 65% of the hydrogenated rosin ester (Foral 105) and the graft copolymer prepared according to Example 36. The same Laminate from pieces of Kraft paper was made, cut, and weighed for testing.

A mixture of 65% of the hydrogenated rosin ester (Foral 105) and one high molecular weight, ungrafted Ethylene / vinyl acetate copolymer "Elvax 260" was manufactured. This mixture was used to make two pieces of Kraft paper for testing as a comparative sample for the above two examples. The results are given in Table XV.

Table XV

Sample temperature at which the

Glued connections are in

example Warming cabinet 42 solved, ⁰ C Comparative sample 65 - 70 Example 41 90 - 95 Example 40 115 - 120

10 g of ethylene copolymer (method M) solved. This hot solution was added 2 ml of a polyethylene oxide containing a polymer a molecular weight of about 360 (about 8 ethylene oxide repeating units), and in which most Chains at one end have a primary amino group (-NH ") and contained an alkyl radical at the other end. (Manufacturer Jefferson Chemical Company, trade name

009 321/0917

25510H

"Amines 4419-35"). The manufacturer provides a molecular weight of 360, based on a primary amine content of 2.71 milliquivalents / g. The received Solution was held at about 110 ° C for 5 minutes. The solvent was evaporated and the solid product pressed as a melt into a clear film.

The infrared spectrum of this sample showed that essentially borrowed all anhydride groups of the ethylene copolymer with the terminal amino groups of the polyethylene oxide chains had reacted.

Example 43

5 g of an ethylene copolymer (method S) were dissolved in hot toluene. This hot solution became 1 g of the same polyethylene oxide with terminal amino groups added. The solvent was evaporated and the solid product as a melt pressed into a 254 .u thick film. The slide was on a Keithly electrometer No. 610B tested according to ASTM D 257. A specific

9
A shear resistance of 10 ohm-cm was determined. in the

In contrast, a comparative sample had that from an ungrafted ethylene / vinyl acetate copolymer

(28% vinyl acetate) consisted of a specific resistance

13th
from 4.4 χ 10 0hm-cm. The graft copolymer had

thus 44,000 times the conductivity of the ungrafted Resin.

Example 44

3 5 g of ethylene copolymer (method R) were mixed with 2 cm of the same polyethylene oxide with terminal amino groups as implemented in Example 42 in the same manner. The test of the solid film showed a specific

7th
see resistance of 6.7 χ 10 ohm-cm. This resin had

thus almost 1,000,000 times the conductivity of the ungepf Ropf th resin according to Example 43.

B09821 / 0917.

Example 45

Production of a polypivalolactone with terminal j

Amino groups I

ι To 51.9 g of 10% aqueous tetrabutylammonium hydroxide j

3.02 g of p-aminophenylacetic acid was added. The he- i

j held solution became a under reduced pressure; amber-colored oil evaporated, the under reduced!

Pressure dried to give a green solid which was washed with tetrahydrofuran.
4.7 g of almost colorless crystals of tetrabutylammonium p-aminophenyl acetate (hygroscopic) were obtained.

To a solution of 50 g of pivalolactone in 100 ml of anhydrous tetrahydrofuran in a 500 ml resin kettle
a solution of 4.7 g of tetrabutylammonium p-aminophenyl acetate in 10 ml of methanol was added with stirring. After 5 minutes, an exothermic polymerization took place under vigorous reflux, the polymer being precipitated.
The polymer was filtered off and twice in one
Waring mixer washed with ethanol and dried at 70 ° C./0.1 mm Hg, 51.7 g of polypivalolactone having terminal amino groups being obtained. The inherent
Viscosity was 0.15 (0.5% in trifluoroacetic acid at

25 ° C). Polymerisa te *
Ί Q * ~ 1 ι * T ¹
'm2 61 C. 8th H 0 H Elemental analysis: 61 Λ 8th , 35 0 , 61 Calculated for one
degree of 42,
^C 234 ^H 380 ° 86 ^N 2 ^: 60 , 3 8th , 28 0 , 42 Found: Differential scanning calorimetry , 9 , 26 , 41 First heating: T 200 ° C.

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Grafting of ethylene / methyl acrylate / ethyl half ester of maleic acid and polypivalolactone containing terminal amino groups

On a two-barrel mixer of 76.2 mm preheated to 225 ° C 24 g of pivalolactone with terminal amino groups were first melted (amber-colored), whereupon 41 g of a copolymer of 54% by weight methyl acrylate, 4.5% by weight of the ethyl half ester of Maleic acid and 40.5 wt .-% ethylene were added. The polymers were kneaded for 13 minutes. Initially, vapors were observed however, the vapor formation soon ceased. 60 g one Amber colored rubbery polymer was obtained. A film was made between polyamide films ("Kapton") by the applicant) pressed at 215 C and 14.06 kg / cm. When the film was stretched at 5.80 cm / min, an elongation at break became of 360% (deformation rest 175%) and a tensile strength of 133.6 kg / cm was determined. A sample that was stretched to 160% three times (after cold drawing) had a set from 15- / 6. A fiber spun at 204 ° C. had a linear density of 209 den, an elongation of 200% and a tensile strength of 0.38 g / den.

A sample of the polymer was cleaned as follows: The sample was ground in a mill with dry ice and then for 1 hour with 300 ml of ethanol containing 300 ml of tetrahydrofuran, and 40 ml of 10% hydrochloric acid mixed. The polymer was in the mixer washed with ethanol and then dried at 60 C / 0.1 mm Hg. The purified polymer was pressed at 200 ° C./1054.5 kg / cm into a clear, yellow, bubble-free film which had an elongation of 400% (elastic elongation 100%) and a tensile strength of 198 kg / cm.

Example 46 .

10 g of ethylene copolymer (similar to the copolymer of the process R) were prepared according to Example 42 with 4 ml Polyethylene oxide with terminal amino groups in the same

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Wise implemented. 4 g of this graft copolymer were

with 46 g of polypropylene ("Profax 6501", manufacturer Hercules, j

Inc.) on an electrically heated two-roll mixer ge j

mixes. The solid product was melt spun to;

Fibers processed. The fibers were made as a tape of 3500 denier

subtracted and checked for resistivity that;

4.8 χ 10 0hm-cm. In contrast, fibers _f

17 I.

made of pure polypropylene an a'ert of about 10 ohm-cm. \

Example 47

A styrene polymer was made using aminoethane thiol as chain transfer agents by radical polymerization according to the Ver-j described in US Pat. No. 3,689,593 drive manufactured. The polymer had a molecular weight of about 3500 (about 34 monomer units). About 90% of the molecules had an NH ^ group at one end and either a phenyl radical or a methyl radical at the other end .

0.5 g of this solid polymer was a solution of 2.5 g of an ethylene copolymer (method S) mixed in in boiling toluene. The solution became a clear folio poured. The clarity of this film indicated that graft polymerization had occurred.

Example 48

6 g of copolymer similar to the polymer prepared according to process M were dissolved in hot toluene. This Solution was 3 g of a low molecular weight polystyrene similar to the polystyrene prepared according to Example 47 added. The polymer was dried to a clear film on the steam bath. The infrared spectrum showed that 20 to 25% of the anhydride present in the ethylene copolymer had reacted.

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Example 49

A low molecular weight polymer of methyl methacrylate was made according to the method described in US Pat. No. 3,689,593 in a 250 ml dog-top flask herg estellt, in which 100 ml of toluene, 75 ml of non-inhibited methyl methacrylate, 0.6 g of 2-aminoethanethiol and 0.1 g of azodicyclohexanecarbonitrile ("Vazo 88") are added became. The mixture was stirred vigorously at 110 ° C. for 1 hour. Unreacted monomer and solvent were aborted. The polymer obtained showed 41% conversion of the methyl methacrylate.

5 g of the ethylene copolymer prepared according to process S. were dissolved in toluene. 1.75 g of the methyl methacrylate polymer described above were added to the solution. The solution was heated to about 100 ° C. for 10 minutes, dried and pressed as a melt into a 0.25 mm thick film. the Foil was crystal clear, tough, and moderately flexible. A comparative sample was made using an ethylene / vinyl acetate copolymer, which contained 28 #> vinyl acetate, instead of the ethylene copolymer prepared according to process S in the case of the above described mixing method used. The received The film was somewhat cloudy and had very poor tear resistance. This comparison shows that the low molecular weight Polymethyl methacrylate in this example does not have an ethylene / vinyl acetate bipolymer is compatible, and that consequently the good physical properties of the product of the The present example show that a graft copolymer has been formed.

Example 50

A low molecular weight polymer of methyl methacrylate was prepared according to the method described in Example 49. The proportion of 2-Aminoäthanthio'ls was 0.4 g and the Temperature lowered to 100 C. 0.1 g of azobisisobutyronitrile (“Vazo 64”) was used as the initiator. The received Polymer showed a conversion of the methyl methacrylate to 51%.

609821/0917

A solution of 5 g of the ethylene copolymer prepared according to process S in toluene was prepared. This Solution was a solution of 5.3 g of the above-mentioned poly

methyl methacrylate in toluene added. The solvent was evaporated and the polymer at 190 C to a film of j 0.25 mm thick pressed. The film was crystal clear, a sign j as well as in the film produced according to Example 49 that! Grafting had taken place.

Example 5 1

£ in a mixture of 90 $ polyvinyl chloride and 1Ο '; ό of the graft copolymer prepared according to Example 50 was prepared on a heated two-roll mixer. The polyvinyl chloride used contained 2% of the stabilizer "Thermolite 31". The mixture was pressed into panels 3.17 mm thick for the tests. The plates were clear. They had a notched Izod impact strength of 5.4 cmkg / cm notch. The dimensional stability under heat under load according to ASTM D-648 (18.6 kg / cm ² ) was 68 ° C.

Example 52

A low molecular weight polymer of methyl methacrylate was made prepared in the manner described in Example 49. The proportion of methyl methacrylate was 47 g and the proportion of 2-aminoethane thiol 0.5 g. The catalyst used was 0.05 g of azobisisobutyronitrile "Vazo 64" used. The mixture was heated to 100 ° C. for 1 hour. The polymer obtained showed $ 36 sales of methyl methacrylate. It had a number mean the molecular weight of about 7000 as determined by vapor pressure osmometry. This corresponds to an average degree of polymerization from about 70.

Example 53

A graft copolymer was based on that described in Example 49 Way from 2 g of the polymer prepared according to Example 52 and 2 g of that prepared according to method V. Polymer produced. From a solution of the product became

609821/0917

cast a clear and flexible film, a sign that grafting had taken place.

Example 54

A mixture was made on a two roll mixer. This mixture contained 85% polyvinyl chloride and 15% according to Example 53 produced graft copolymer. That The product had a notched Izod impact strength of 13 cmkg / cm Notch and an impact strength determined in the ball drop test of 122 cmkg / mm thick (plate of 0.76 mm thick).

Example 55

A low molecular weight polymer was in the manner described in Example 49 from 47 g of methyl methacrylate, 0.4 g 2-aminoethanethiol and 0.04 g of azobisisobutyronitrile "Vazo 64". The polymer obtained showed 33% conversion of the Methyl methacrylate. It had a number average molecular weight of 5500 as measured by vapor pressure osmometry.

Example 56

A graft copolymer was based on that described in Example 49 Way from 2.4 g of the polymer described in Example 55 and 3.7 g of a polymer containing 32% vinyl acetate and contained 2.6% maleic anhydride. The film was clear and rubbery. The infrared spectrum showed that essentially all anhydride groups were converted.

Example 57

A mixture was made in the manner described in Example 51 made from 85% polyvinyl chloride and 15% of the product of Example 56

manufactured. This mixture had a flexural modulus of

2.

23902 kg / cm, an Izod notched impact strength of 12 cmkg / cm

cm notch, an impact strength in the ball drop test of 122 kg / and a dimensional stability under heat of

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25510H

Example 58

• A solution of 5 g of the maleic anhydride containing! Ethylene copolymer prepared according to process Q in toluene was prepared. This solution was 2 g of polypropylene oxide!

i added, the chains of which are essentially all an alkyl-I remainder with 3 C-atoms on one find and a primary amino groupj contained at the other end ("Jeffamine 4419-69", manufacturer i Jefferson Chemical Co., molecular weight about 600). The solvent was removed by heating on the steam bath. One off Solution cast film of this product was clear, an indication that grafting had occurred.

Example 59

1 g of the ethylene copolymer prepared according to process S was dissolved in hot hexamethylphosphoramide. Furthermore were 0.5 g of a low molecular weight polycaprolactam (method GG) dissolved in hot hexamethylphosphoramide. The two solutions were mixed and kept hot for about 5 minutes. The polymer was precipitated in pentane, filtered off and washed with pentane and dried. A film pressed from the melt of this polymer was clear. The infrared spectrum showed that about 50% of the anhydride groups in the ethylene copolymer react had.

1 g of this half-grafted copolymer was again in dissolved hot hexamethylphosphoramide. 0.5 g of the short-chain polyethylene oxide prepared according to Example 42 were added to this solution added. The mixture was again kept hot for about 5 minutes. The polymer was precipitated, filtered off, washed and dried. The infrared spectrum shows * <* by the absence of the infrared band at 5.4 u that the entire Anhydride had been converted.

In this experiment, a graft copolymer was obtained, whose main chain consists of an ethylene / vinyl acetate / maleic anhydride copolymer existed, and that two types of side chains, namely a polyamide chain and a chain made of poly-

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2551QU

ethylene oxide units contained.

Example 60

Hot toluene was used as the reaction medium in which a short chain of polymethyl methacrylate units similar to the Product of Example 49 on the ethylene copolymer prepared according to method S were grafted. The dried sample was pressed into a clear film using the infrared spectrum showed that about 10% of the anhydride groups had reacted.

0.75 g of this graft copolymer were again in toluene solved. 0.25 g of the short-chain polyethylene oxide prepared according to Example 42 were added to the solution. The solution was kept hot for 5 minutes and then dried. The pressed film was clear, the infrared spectrum showed completely Reaction of the anhydride.

In this experiment, a graft copolymer was obtained, whose main chain consists of an ethylene / ^ inyl acetate / maleic anhydride copolymer existed, and that two types of side chains, namely a polymethyl methacrylate chain and a Polyethylene oxide chain.

Example 61

In the same manner as described in Example 60, 0.5 g of a short chain polystyrene similar to that in Example 47 described on 1 g of the ethylene copolymer prepared according to process S grafted. On 0.75 g of this partially grafted copolymers were grafted 0.25 g of the polyethylene oxide prepared according to the example.

In this experiment, a graft copolymer was obtained, an ethylene / vinyl acetate / maleic anhydride copolymer as the main chain and both side chains made of polystyrene as well Contained side chains made of polyethylene oxide.

609821/03 17

.85-25510H

Example 62

In the manner described in Example 60, 2 g of the polymethyl methacrylate resin prepared according to Example 49 were included 1 g of the ethylene copolymer prepared by process S reacted. The infrared spectrum of this copolymer showed that about 40% of the anhydride had reacted.

1 g of the short-chain polystyrene resin, which was similar to that described in the example, was grafted onto 1.5 g of this partially grafted copolymer. The film pressed from this graft copolymer was clear. The infrared spectrum showed that about 90% of the anhydride groups consisting of grafting _a re had yaws.

In this experiment a graft copolymer was produced, in which about 50% of the total number of side chains are polymethyl methacrylate chains and about 50% of the total side chains are polystyrene side chains.

Example 65

An ethylene copolymer was prepared which, according to analysis, contained 23% vinyl acetate and 9% methyl hydrogen maleate (methyl half ester of maleic acid). A solution of 1.5 g of this copolymer and 1 g of a polyethylene oxide, the terminal Containing amino groups and having a molecular weight of about 1000 was made in toluene. This l'olyethylene oxide was similar to the polyethylene oxide prepared according to Example 42. The solution was heated for about 15 minutes and then to the Stripping off the solvent treated on the steam bath. The infrared spectrum showed that grafting had taken place.

Example 64

A styrene copolymer which contained 17% by weight of polymerized maleic anhydride was used ("Lyntron 820", manufacturer Monsanto). 2 g of this copolymer, which was dissolved in toluene / tetrahydrofuran (90:10), were mixed with 3.6 g of the

609821/0917

-84- 25510U

Measured example 63 produced polyethylene oxide (molecular weight 100O) reacted with terminal amino groups. The dried one Mixture was perfectly clear, a sign that grafting had occurred.

Example 65

In the manner described in Example 64, 2 g of the styrene / maleic anhydride copolymer prepared according to Example 64 were obtained with 2.2 g of the polypropylene oxide prepared according to Example 60 (molecular weight 600) with terminal Amino groups implemented. The dried mixture was perfectly clear, an indication that grafting had occurred.

Example 66

1 g of the styrene / maleic anhydride copolymer prepared according to Example 64, which was dissolved in hexamethylphosphoramide was made with a polycaprolactam oligomer having a molecular weight of 1140 and contained terminal amino groups (Method DD), implemented. The polymer obtained formed a clear film, a sign that grafting was taking place would have.

(Ethylene / maleic anhydride) / caprolactam graft copolymer

A) Solving procedure Example 67

A solution of 10 g of a ^ opolymerisats of 95.8% ethylene and 4.2% maleic anhydride (E / MAnh) (melt index = 15) in 125 ml of toluene and 25 ml of hexamethylphosphoramide (HMP) was with a solution of 3.7 g caprolactam (CL) / hexylamine (HA) oligomer (degree of polymerization = 7; Table VIII, method FFF) mixed in 100 ml of dry HMP at 105 C. The mixture was stirred at 100-110 ° C. for one hour. The reaction mixture was then partially cooled and the polymeric product precipitated and isolated by successively adding two portions of 15 ml each Methanol were added, the mixture brought to room temperature

809821/0917

_ ₈ . 25510H

cools and was diluted with 300 ml of methanol to precipitate the graft copolymer. The polymer was filtered off and then successively in a mixer twice with methanol, twice with water and then twice with methanol washed. The vacuum dried product (11.2 g) showed endothermic melt energy values by differential scanning calorimetry at 106 C (olefin maximum) and 187 C (amide maximum). It was pressed into a 0.13 mm thick film, which was clear, transparent and flexible, a sign that an (E / MAnh) / CL-j graft copolymer had been formed. The slide had

2 a tensile strength (T) of 143 kg / cm, an elongation (D) of 280% and a modulus of elasticity (M) of 1930 kg / cm. Pressed

Bars had a flexural modulus of 2600 kg / cm at 25 C,

9 η kg / cm ^ _n

1270 kg / cm at 60 C and 548 / at 100 C. The analysis for nitrogen resulted in a CL / HA content of 21% by weight.

The experiment described above was carried out with 10 g of the 95.8 / 4.2 E / MAnh copolymer (melt index = 15) and 7.3 g of the CL / HA oligomer (degree of polymerization = 15) of Table VIII, Method BBB. The (E / MAnh) / Cl graft copolymer obtained analysis contained 40% CL / HA endothermic melt energy values according to differential scanning calorimetry of 106 C and 207 C and showed a thickness as a film

2 of 0.13 mm, a tensile strength of 178 kg / cm, an elongation

2 of 87% and a modulus of elasticity of 4060 kg / cm. Pressed bars had flexural modulus values of 6190 kg / cm ² at 25 ° C, 2390 kg / cm 2 at 60 ° C and 1400 kg / cm ² at 100 ° C.

B) roller mixer process (reaction in the melt) Example 68

On a two-roll mixer heated electrically to 205 ° C with 76.2 mm folds, 40 g of copolymer of 95.8% ethylene were obtained and 4.2% maleic anhydride (melt index = 15) kneaded under flowing nitrogen until the copolymer has melted was. Finely divided CL / HA oligomer (9.7 g; degree of polymerization = t 10; prepared as in Table VIII, procedure DDD) was sprinkled into the molten polymer, whereupon

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25510U

kneading was continued for about 6 minutes. The kneaded product (48 g) was then taken off the roller mixer and cooled. The analysis showed a CL / HA content of 19% by weight. From the Graft copolymers were 0.13 mm at 240 to 260 ° C pressed thick foils that were clear, transparent, pliable and kinkable. The infrared spectrum indicated the presence of Amide and anhydride groups. The foils had a tensile strength

2
of 135 kg / cm, an elongation of $ 306 and an elastic

2 modulus of strength of 2180 kg / cm.

The experiment described above was carried out with the same Xethylene / maleic anhydride copolymer, various caprolactam / hexylamine oligomers and at various temperatures of the roller mixer repeatedly. All products produced clear, transparent films, a clear indication that a grafted (E / MAnh) / (CL / HA) copolymer had been formed. The details of the experiments and the results are given in Table XVI called.

609821/0917

Table XVI .

Production of (ethylene / maleic anhydride) / caprolactam graft copolymers

on the roller mixer

At- E / MAnh CL / HA-Oligomeres Temp. Graft copolymer

play g (I- (a) ° C _{CL / H} A ^(b) T _n Deh- module bending DSC-

68 beiSD.) Ε (PG); -, —2: ■ —2,,

% kg / cm voltage kg / cm module Maxima

% kg / cm ^{2 °} C

σ> 25 ° c

g A 40.0 ^! AAA 8.0 7 ¹ ^ ^{0 1β} ί ¹⁷ ) "", - 2250 107,

S. ₃ C "c> ^ oO AAA 11.1 7 210-215 25 (27) Ι46 230 2240 2460 103,

J C 30.0 BBB 22.0 15 220-225 40 (42) 173 73 4290 4430 109.207

iS. D ^ ^c) 5O.O - 29.Ι 20 225-230 (49) 214 116 4150 569Ο

* "* e ( ^c) 30.0 - 29.Ι ^{20 2} ^ ⁰ (^ ¹⁹ ° 75 4400 6260

_F (c) 30.0 - 9.8 5.8 190-200 (25) 155 360 20Ö0 2390

(a) From Table VIII.

(b) Based on % N in the kneaded product. ied in brackets are the quantities used.

. . cn

(c) Base polymer and oligomer premixed before being fed to the roller mixer. -. (j- \

C) extrusion process (reaction in the melt) Example 69

A mixture of 65 parts of a copolymer of 93.8% ethylene and 6.2 % maleic anhydride (melt index = 5.1) and 35 parts of a CL / HA oligomer (degree of polymerization = 7; Table VIII, method AAA) was at 225 ° C given by a twin-screw mixing extruder. The throughput time was about 4 minutes. A clear melt was obtained as the extrudate, a sign that the grafting reaction had taken place satisfactorily in a single pass. The product

2 had a flexural modulus of 2030 kg / cm and the following

2-9

Torsional modulus values (dynes / cm 10) at various temperatures: 12.4 at -180 ° C; 8.0 at -100 ° C; 5.1 at -50 ° C; 2.3 at 0 ° C; 1.37 at 20 ° C; 0.61 at 50 ° C; 0.16 at 100 ° C; 0.08 at 150 ⁰ C.

Further (E / MAnh) / CL graft copolymers were prepared using the method described above. The details and results are shown in Table XVII below.

609821/0917

ω ο co co κ »

Table XVII Production of (ethylene / maleic anhydride) / caprolactam profm copolymers in the extruder

At-

^Game 69 MI *

A B c

E / MAnh

CL / HA oligomeric flexural modulus ⁽ < ²

/G

MAnh ^(a) E / MAnh ^(b) Author (PG) (%) ^(b)

9.3 5.9 9 *

kk 3h

AAA 18 18

56 66 2-9 modulus of torsion, dynes / cm x10

-180 -100 -50 0

Op Op Op Op

20 50 100 I50 ^{! 0} C. ⁰ C. ⁰ C. ⁰ C.

2Ö10 12.0 8.1 6.0 3.0 2.1 0.88 0.3 ^ 0.21

15.5 9.5 7Λ 5.0 kO 2.8 0.70 O.iiO

16.0 9.1 7.1 5.0 U.o '2.6 0.72 0.38

(a) Percent MAnh in the E / MAnh base copolymer

(b) Fraction of the active participant in the extrusion mixture. *) MI = melt index cn -cn

25510H

Example 70 (ethylene / ethyl maize eat) / caprοlactam graft copolymer

A mixture of 18 g copolymer of 91% ethylene and 9% Monoethyl ester of maleic acid (ξ / ΜΑΜΕ) and 5.1 g of CL / HA oligomer (Degree of polymerization = 6.7) was on a two roll mixer kneaded as in Example 68. The (E / MAME) / CL graft copolymer obtained could be added to the cold roller mixer be rolled out in a flexible fur. The analysis showed I

a CL / HA content of 22%. The product had the following j

2 —9 ί

Torsional modulus values (dynes / cm χ 10) at different tempera-j doors: 11.9 at -180 ° C; 9.4 at -100 ° C; 8.2 at -50 ° C; 5.2 at 0 ° C; 3.8 at 20 ° C; 2.6 at 50 ° C; 0.90 at 100 ° C; 0.14 at 150 ° C.

Example 71 (ethylene / butyl itaconate / caprolactam graft copolymer

The solution procedure described in Example 67 was generally followed followed. Here, 7 g of copolymer of 88.3% ethylene and 11.7% monobutyl ester of itaconic acid (E / Bult) dissolved in 100 ml of toluene at 100 to 115 ° C. After adding of 25 ml of HMP became a solution of 3.7 g of CL / HA oligomer (Degree of polymerization = 6.7) in 75 ml of HMP was added all at once with vigorous stirring. Then another 1.25 Stirred and heated for hours. The Profpmischpolymerisat was then precipitated and isolated by adding 400 ml of methanol. j The analysis of the product (8.2 g) showed a CL / HA content of 23% by weight. Films pressed at 235 to 240 C were clear, transparent and flexible.

(Ethylene / maleic anhydride) / laurolactam graft copolymer

Example 72

Following the solution procedure described in Example 67 was produced a number of (E / MAnh) / LL graft mixers. The data are presented in Table XVIII below.

609821/091 7

Table XVIII (E / MAnh) / LL graft polymers

at Base polymer MI * S. LL / HA oligomer PG G Graft copolymer the end
prey
G % DSC
Enamel.
punk: t, ° C Bend
module
kg / cm ² I. - I. game
72 MAnh
% 174 7.0 Ver
travel 6.5 9.6 14.8 - 160 ^ i - VD
t- » A- 9.8 5 10.0 MMM 6.5 8.7 17.1 - 160. 2900 I. B. 6.2 15th 10.0 MUSK 7.2 6.54 14.9 39 163-5 3070 C. 4.2 40 10.0 NIiN 7.2 4.55 13.0 31 - D. 3.0 40 10.0 NNN ' 6.4 2.5 10.7 18th 160 E. 3.0 40 10.0 - 6.4 1.5 10.2 14th 159 Cn
cn F. 3.0 Melt index - * MI =

Example 73

An ethylene / maleic anhydride base copolymer containing 86.5% by weight of ethylene and 13.5% by weight of maleic anhydride, was produced. The copolymer was pumped through a tube heated to about 500 ° C. using an extruder to lower the molecular weight. The melt viscosity was 600 cPs at 140 C. The average chain length was about 300 carbon atoms.

1 g of the basic copolymer was mixed with 2 g of the caprolactam / laurolactam oligomers prepared according to method 00 with terminal Amino groups reacted in hot hexamethylphosphoramide. The solution was kept hot for about 5 minutes and then poured into cold pentane, which was stirred quickly, to precipitate the polymer. It was then filtered off and to remove excess solvent with acetone | washed and dried.

The basic copolymer of the graft copolymer contains im Average only about 3 sites per chain that are reactive with amino groups. The side chain polymer has on average a chain length of about 2/3 the length of the base copolymer. On average there are three polymeric side chains grafted onto the base copolymer.

The production of graft copolymers whose basic copolymer is a crystalline copolymer of ethylene with is a comonomer which is reactive with amino groups Forms, and whose side chains are either polycaprolactam or polylaurolactam chains, is shown in the following Examples described. All of these graft copolymers have two melting points.

$ 09821/0917

Example 74

. In a shaking tube, 50 g of caprolactam with 10 g n-Hexylamine reacted at 250 C, with an oligomer with an average degree of polymerization of 7 was formed.

anhydride This oligomer was made with a 4.2% maleic acid / containing

I ethylene copolymer, which had a melt index of about 5, ι

ο '

mixed on the roller mixer at 225 C under nitrogen. The mixture contained 16% polyamide. After mixing for 2 minutes the melt became transparent. The product was pressed into transparent films or rods, the DTA melting points of 107 and 178 ° C.

Example 75

The experiment described in Example 74 was repeated with the difference that 40% of an oligomer of caprolactam with | an average degree of polymerization of 15 were used. i It took about 4 minutes on the roller mixer to ^(form a transparent melt. The product had DTA-I

Melting points of 107 ° and 207 ° C. !

In a twin screw extruder 5 parts of this graft ' copolymers with 80 parts of polycaprolactam ("Plaskin;

. mixed j 8200 ") and 20 parts of high density polyethylene (" Alathon 7050 ") A _us d _em mixture were prepared by injection molding test specimens with the following properties: flexural modulus 20,180 kg / cm; Yield strength 572 kg / cm; tensile strength 638 kg / cm; elongation at break 250%; notched Izod impact strength 7621 cmg / cm. A surface formed by cracking a specimen in liquid nitrogen was observed with a scanning electron microscope. 3 to 0.5 µm in diameter, and the bond strength between the nylon and the polyethylene was good.

609821/0917

255T014

Example 76

The experiment described in Example 74 was repeated with the difference that 25% of an oligomer of caprolactam with an average degree of polymerization of 5.8 was used. The graft copolymer had DTA melting points of 106 and 177 ° C.

Example 77

35% of an oligomer made from caprolactam and n-hexylamine with an average degree of polymerization of 7 was with an ethylene copolymer containing 6.2% maleic anhydride and had a melt index of 5.1 in a single pass through a twin screw extruder at 225 ° C

implemented. The graft polymer was transparent and

2 had a flexural module of 2032 kg / cm. The DTA melting points

were at 97 ° and 182 ° C.

A mixture was made of 75 parts nylon-66 ("Zytel 101 '·), 25 parts of high density polyethylene ("Alathon 7050") and 2 parts of the copolymer prepared according to this example manufactured. The pressed mixture was as follows

2

Properties: flexural modulus 25240 kg / cm; Yield strength 526 kg / cm

2 tensile strength 443 kg / cm; Elongation at break 200%; Notched Izod

tenacity 6532 cmg / cm. The polyethylene spheres had one Diameters from 0.2 to 0.5 u Adhesion between nylon and polyethylene was good.

Example 78

The experiment described in Example 77 was repeated with the difference that the polyamide content was 46% and that Ethylene copolymer contained 9.8% maleic anhydride and had a melt index of 126. The graft copolymer had the following properties: flexural modulus 2812 kg / cm; Yield point 170 kg / cm; Tensile strength 172 kg / cm; Elongation at break 120%. The DTA melting points were 104 and 178 ° C.

609821/0917

Example 79

In a twin screw extruder, an ethylene copolymer containing 5.7% maleic anhydride and a melt! index of 4.4, with 33% of an oligomer composed of caprolactam and n-ilexylamine had been prepared and a middle one Degree of polymerization of 6.7 had reacted at 225 ° C., a graft copolymer being formed. One through

Press-made sheet 0.35 mm thick had one

2 modulus of elasticity of 2039 kg / cm, a tensile strength of

253 kg / cm and an elongation of 50.5%. The film was stretched twice at 104 ° C. in each direction, one being 0.09 mm thick film was obtained, which has a modulus of elasticity of

2 2

7101 kg / cm, a tensile strength of 809 kg / cm and an elongation of 59% had. When the biaxially stretched film was 101 was heated to 120 C, it shrunk so that its area was reduced by 31 to 38%. The DTA melting points were at about 100 ° and 184 ° C.

Example 80

An ethylene copolymer containing 9.0% by weight ethyl hydrogen maleate contained, was with 22% of an oligomer, which had been prepared from caprolactam and n-hexylamine and a medium Degree of polymerization of 6.7 had reacted on the two-roll mixer at 225 ° C. A transparent graft copolymer was educated. The DTA melting points were 113 ° and 180 ° C.

Example 81

An ethylene copolymer which contained 5.2% by weight of maleic anhydride and had a melt index of 105 was 40% of an oligomer made from laurolactam and n-hexylamine with an average degree of polymerization of 5.9 on a two-roll mixer reacted at 175 C, with a graft copolymer with a flexural modulus of 7874 kg / cm at 23 C, 5238 kg / cm at 60 ° C and 2742 kg / cm at 100 ° C. if 3.2 mm thick sticks scored with a razor blade,

609821/091 7

sharply bent and immersed in an aqueous solution of 50% by weight Zinc chloride were immersed at room temperature, it took 34 days for 4 rods before cracking occurred (ASTM D-1693-70, modified). With three wands it took 42 days and with a stick more than 68 days before cracking occurred. The DTA melting points were 98 ° and 160 ° C. The graft copolymer is suitable for the production of flexible hoses.

Example 82

An ethylene copolymer containing 4.5% maleic anhydride and had a melt index of 180, was in an extruder with 25% of an oligomer prepared from laurolactam and n-hexylamine with an average degree of polymerization of 6.35 implemented. The graft copolymer had a

2

Flexural modulus of 3719 kg / cm, a tensile strength of 162 kg / cm and an elongation at break of 90%. The embrittlement temperature, determined according to ASTM method D 746-73, was below -76 ° C. the DTA melting points were 105 ° and 155 ° C. This graft copolymer is suitable for the production of flexible hoses.

Example 83

An ethylene copolymer containing 10.4% maleic anhydride and had a melt index of 92, was reacted with 40% of a caprolactam oligomer which had a medium Had a degree of polymerization of 7 and was made without amine and both terminal carboxyl groups and terminal amino groups contained. The reaction was carried out on the roller mixer at 225 ° C. The melt was in 60 seconds clear and transparent. The DTA melting points of the graft copolymer were 95 and 195 C.

609821/0917

Example 84

The experiment described in Example 83 was repeated with the difference that the oligomer of caprolactam and n-butylamine was produced and an average degree of polymerization of 6.5 had. The time until the melt became clear on the roller mixer at 225 ° C. was 35 seconds. the DTΑ melting points of the graft copolymer were 80 and 19O ° C.

Example 85

The experiment described in Example 83 was repeated with the difference that the oligomer of caprolactam and n-Octadecylamine was produced and an average degree of polymerization of 6 had. The melt became clear after 35 seconds on the roller mixer at 225 ° C. The DTA melting points des / copolymers were 99 and 193 C. Graft

Example 86

An ethylene copolymer, which contained 19% ethyl hydrogen maleate and had a melt index of 180, was on the roller mixer with 35% one made from caprolactam and n-hexylamine Oligomers reacted with an average degree of polymerization of 7.7. The graft copolymer had DTA melting points of 87 and 192 C, a flexural modulus of 3902 kg /

2 2

cm, a tensile strength of 224 kg / cm and an elongation at break

of 170%.

Example 87

The experiment described in Example 86 was repeated with the difference that the ethylene copolymer was 29% butyl hydrogen itaconate and had a melt index of 290. The graft copolymer had DTA melting points of 99, 186 and 210 C, a flexural modulus of 3269 kg / cm, a tensile strength

2 '

of 163 kg / cm and an elongation at break of 190%.

609821/0917

25510H

Example 8 8

An ethylene copolymer containing 17% ethyl hydrogen maleate and had a melt index of 92, was made in an extruder with 25% of one of laurolactam and n-flexylamine Oligomers reacted with an average degree of polymerization of 5.34. The graft copolymer had DTA melting points of 100 and 150 C, a flexural modulus of 2615 kg / cm, a tensile strength of 256 kg / cm and an elongation at break of 230%. It is suitable for the production of flexible hoses.

609821/091 7

Claims (16)

Patent claims Process for the production of thermoplastic graft copolymers, characterized in that one a) a basic copolymer composed of at least two monomers, at least one of which is reactive with amino groups Positions in the form of an anhydride group, a vicinal pair of carboxyl groups and / or a carboxyl group, which is adjacent to an alkoxy carbonyl group, the alkoxy radical having up to 20 carbon atoms contains and at least one of the monomers has no sites reactive with amino groups, and b) at least one side chain polymer which has one reactive amino group per chain selected from the primary and contains secondary amines existing group, while the rest of the side chain polymer with the reactive Places the base polymer is essentially unreactive, Heated with mixing for about 15 seconds to 60 minutes. 2. The method according to claim 1, characterized in that an elastomeric base copolymer is used. 3 · The method according to claim 1, characterized in that an essentially crystalline base copolymer is used. 4. The method according to claim 1 to 3, characterized in that that it is carried out in the melt. 5. The method according to claim 1 to 3, characterized in that it is carried out in solution. 6. The method according to claim 1 to 5, characterized in that the side chain polymer is a polymer or Copolymer of one or more lactams with 3 to 12 carbon atoms, one polymer or one copolymer 809821/0917 or several organic oxides with 2 to 16 carbon atoms, a polylactone, a polystyrene, a substituted polystyrene, a copolymer of styrene with substituted Styrene, a polyacrylate, a polymethacrylate and / or a copolymer of an acrylate with a Methacrylate used. 7. Thermoplastic graft copolymers containing a basic copolymer of at least two monomers, of which at least one sites reactive with amino groups in the form of an anhydride group, a vicinal one A pair of carboxyl groups and / or a carboxyl group which is adjacent to an alkoxycarbonyl group, wherein the alkoxy radical contains up to 20 carbon atoms and at least one of the monomers does not contain any amino groups whereby
has reactive sites / short-chain polymer side chains containing 5 to 60 recurring units are bound to the basic copolymer via amide or imide bonds, which are of short-chain polymers which contain a primary or secondary amino group, but are essentially free of other groups which are reactive with amino Sites can react, are derived, and the imide or amide bonds have been formed by reaction of the primary or secondary amino groups with the sites of the basic copolymer which are reactive with amino groups. 8. Graft copolymers according to claim 7 * thereby characterized in that the side chains are polyamide side chains and both the base copolymer and the final graft copolymer are elastomeric. 9. Graft copolymers according to claim 7 , characterized in that the side chain polymer is a polymer or copolymer of one or more lactams having 3 to 12 carbon atoms, a polymer or copolymer of one or more organic oxides having 2 to 16 carbon atoms, a polylactone, a Polystyrene, a substitute 609821/0917 ated polystyrene, a copolymer of styrene with a substituted styrene, a polyacrylate Polymethacrylate or a copolymer of an acrylate with a methacrylate is. 10. Graft copolymers according to claim 7> characterized in that the side chain polymer is a polycaprolactam, a polylaurolactam and / or a Copolymer of caprolactam with laurolactam is. 11. Graft copolymers according to claim 7 > characterized in that the side chain polymer is polyethylene oxide or polypropylene oxide. 12. Graft copolymers according to claim J, characterized in that they are essentially crystalline. 13 graft copolymers according to claims 1 to 12, characterized in that the basic copolymer is a copolymer of ethylene, an α-01efin, a monoreactive diene and maleic anhydride. 14. Graft copolymers according to claim 7 to 13, characterized in that the base polymer contains propylene as the α-olefin and 1,4-hexadiene as the diene. 15 · Plastic graft copolymers containing a Grundcopolymerisat from 70 to 99 wt -.% Ethylene and a comonomer having reactive with amino groups bodies in the form of an anhydride group, a vicinal pair of carboxylic groups and / or a carboxyl group with an alkoxycarbonyl group having up to 20 C-atoms in the alkoxy radical is adjacent, with the basic copolymer via amide or imide bonds polycaprolactam or polylaurolactam side chains, which have an average degree of polymerization of 5 to 30 and terminal N-alkylamide groups with 1 to 609821/0917 25510U 18 carbon atoms in the alkyl radical are bound, and the graft copolymers contain 15 to 50 wt .- ^ polyamide and have two melting points determined by thermal differential analysis (DTA), of which one at 85 to 115 ⁰ C and the other in presence is polycaprolactam side chains at least 165 ⁰ C and in the presence of polylaurolactam side chains at least 15O ⁰ C. 16. Graft copolymers according to claim I5, characterized characterized in that the polyamide side chains have an average degree of polymerization of 6 to 10. 609 821/0917