阅读说明：本技术 作为橡胶替代物的交联塑性体 (Crosslinked plastomers as rubber substitutes ) 是由 贾里-朱西·罗斯基涅米 杰伦·奥德尔柯克 奥斯卡·普列托 斯蒂芬·赫尔斯特罗姆 塔尼亚·皮尔 于 2019-09-30 设计创作，主要内容包括：一种包括聚合物组合物的制品,其中聚合物组合物可通过用包括可水解的硅烷基团的共聚单体单元对乙烯共聚物进行接枝获得,其中聚合物组合物显示出高凝胶含量和在-25℃下低的压缩变定。这些制品应用于汽车挡风雨条,诸如用于门、行李箱和引擎盖的密封系统。(An article comprising a polymer composition obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups, wherein the polymer composition exhibits a high gel content and a low compression set at-25 ℃. These articles find application in automotive weatherstrips, such as sealing systems for doors, trunks, and hoods.)

1. An article of manufacture comprising

A polymer composition comprising a blend of a polymer and a metal,

wherein the polymer composition is obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups,

and

wherein the polymer composition has the comonomer units comprising hydrolysable silane groups in an amount of greater than 0.5 wt%, based on the total weight of monomer units in the polymer composition,

wherein the ethylene copolymer comprises alpha-olefin comonomer units having from 6 to 12 carbon atoms,

and

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-every 100000 CH_nTotal unsaturation of 20 to 100 unsaturated bonds of the group.

2. The article of claim 1, wherein the ethylene copolymer comprises 10 to 50 wt% alpha olefin comonomer units having 6 to 12 carbon atoms, preferably 20 to 45 wt% alpha olefin comonomer units having 6 to 12 carbon atoms, and most preferably 30 to 40 wt% alpha olefin comonomer units having 6 to 12 carbon atoms (as determined using NMR), based on the total amount of monomer units in the ethylene copolymer.

3. The article of claim 1 or 2, wherein the alpha olefin comonomer units are selected from 1-octene or 1-hexene, preferably wherein the alpha olefin comonomer units are selected from 1-octene.

4. The article of any one of claims 1 to 3, wherein the ethylene polymer has a ratio of vinyl groups to total unsaturated groups of less than 0.6 and preferably from 0.3 to 0.1.

5. The article of any one of claims 1 to 4, wherein the ethylene copolymer has a ratio of cis groups to trans groups of greater than 1 and preferably greater than 2.

6. The article of any one of claims 1 to 5, wherein the ethylene copolymer has a crystallinity of between 5% and 8% as measured by DSC using a cooling and heating rate of 50 ℃/min.

7. The article of any one of the preceding claims, wherein the polymer composition comprises an additional polymer component.

8. The article of any one of the preceding claims, wherein the polymer composition is crosslinked after forming the article by hydrolyzing the silane groups in the presence of a Silanol Condensation Catalyst (SCC),

wherein the Silanol Condensation Catalyst (SCC) used in the cross-linking step is preferably a sulfonic acid, more preferably wherein the silanol condensation catalyst is an aromatic organic sulfonic acid which is an organic sulfonic acid and comprises the following structural elements:

Ar(SO₃H)_x (IV)

wherein Ar is a substituted or unsubstituted aryl group and, if substituted, suitably has at least one hydrocarbyl group comprising up to 50 carbon atoms, and wherein x is at least 1;

or wherein the structural element is a precursor of a sulphonic acid of formula (IV) comprising an anhydride of a sulphonic acid of formula (IV) or a sulphonic acid of formula (IV) which has been provided with a hydrolysable protecting group, for example an acetyl group which can be removed by hydrolysis.

9. The article of claim 8, wherein the article has a compression set after crosslinking of 0% to 5% when measured at-25 ℃ (ISO 815-1:2010-9 at-25 ℃).

10. The article of any one of claims 8 or 9, wherein the article after crosslinking has a compression set (ISO 815-1:2010-9 at 23 ℃) of 0% to 20%, preferably 0% to 15%, most preferably 0% to 12.5%, when measured at 23 ℃.

11. The article of any one of claims 8 or 9, wherein the composition after crosslinking has a gel content of 75% to 99%, preferably 90% to 99%.

12. The article of any one of the preceding claims, wherein the ethylene copolymer has an MFR in the range of 0.01 to 5.0g/10min, preferably in the range of 0.25 to 1.25g/10min, more preferably in the range of 0.25 to 1.20g/10min₂(ISO 1133；190℃；2.16kg)。

13. A method for producing an article, comprising the steps of:

a) there is provided an ethylene copolymer having a high molecular weight,

wherein the ethylene copolymer comprises alpha-olefin comonomer units having from 6 to 12 carbon atoms,

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-every 100000 CH_nThe total degree of unsaturation of the groups 20 to 100 unsaturated bonds,

b) obtaining a polymer composition by grafting a comonomer unit comprising hydrolysable silane groups to the ethylene copolymer with a grafting agent such as VTMS to obtain a polymer composition having from 0.5 to 10 wt% of a comonomer unit comprising hydrolysable silane groups,

c) blending the silane-grafted polymer composition from step b) with a silanol condensation catalyst,

d) forming the composition from step c) into an article.

14. The method of claim 13, wherein after step D), the article is crosslinked in the presence of water to obtain a gel content of 75% to 99% (measured according to ASTM D2765-01, method a).

15. Use of a polymer composition for reducing the permanent set (compression set measured according to ISO 815-1: 2010-9) of a crosslinked article compared to a crosslinked article comprising an ethylene copolymer having a lower level of unsaturation:

wherein the polymer composition is obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups,

and

wherein the polymer composition has the comonomer units comprising hydrolysable silane groups in an amount of greater than 0.5 wt%, based on the total weight of monomer units in the polymer composition,

wherein the ethylene copolymer comprises alpha-olefin comonomer units having from 6 to 12 carbon atoms,

and

wherein the ethylene copolymer is characterized by having:

840 to 890 kg-m³The density of (a) of (b),

-every 100000 CH_nTotal unsaturation of 20 to 100 unsaturated bonds of the group.

Technical Field

The present invention relates to an article comprising a polymer composition having an excellent compression set, especially at low temperatures. The invention also relates to a process for producing the article and to the use of a polymer composition comprising the ethylene copolymer for reducing the permanent deformation of the article.

Background

Soft, crosslinked polyolefins are useful as rubber substitutes in many applications. To control the crosslinking of the polyolefin, it may be grafted with silane, followed by crosslinking using a Silanol Condensation Catalyst (SCC).

To make elastic materials, the starting polyolefin, i.e. the ethylene copolymer according to the invention, should have a low density and a low crystallinity or optionally be completely amorphous. The density of the ethylene copolymers is generally reduced by increasing the amount of comonomer. Comonomers having a chain length greater than 6 carbon atoms (e.g., longer chain length comonomers) prevent crystallization of the backbone. The synthesis of the low crystallinity copolymer is optionally performed using a single site catalyst that randomly introduces monomers to form a uniform polymer structure.

Typically, the ethylene copolymer is then grafted with, for example, VTMS using a peroxide in a reactive extrusion process. The peroxide randomly abstracts hydrogen from the polymer chain, allowing the VTMS to react with the polymer. In the grafting reaction, the VTMS reacts randomly at multiple sites in the polymer chain.

EP 0756607B 1 relates to shaped articles comprising silane-crosslinked blends of polyolefin elastomers and crystalline polyolefin polymers. In particular, this document relates to a composition having a viscosity of greater than 850kg/m³Ethylene polymer (typically a copolymer) of density (iii). These materials exhibit desirable tensile strength and/or compression setPerformance, and good elasticity and shrinkage properties. This document describes an ethylene polymer prepared by the following steps: (i) blending a low density polyolefin elastomer with a crystalline polyolefin polymer, (ii) grafting the blend with a silane crosslinking agent (such as VTMS), (iii) shaping the silane-grafted blend into a shaped article, and (iv) curing the shaped, silane-grafted blend with water, preferably in the presence of a condensation catalyst (e.g., a silanol condensation catalyst). This document is concerned in particular with the production of articles which can be used as cable sheaths; in addition, this document describes that the material produced by the above-described method can be used as a flexible weather strip, a fabric, a shoe sole, a gasket, and the like. Further, the silane-grafted ethylene polymer produced by the above process can be formed into a weatherproof part for an automobile; in particular, because the material is clear/transparent, the ethylene polymer can be used as a sealing system for doors, trunks and hoods and the like.

EP 0944670B 1 relates to a crosslinkable polymer composition and in particular such a composition wherein crosslinking takes place via vinylsilane moieties. This document relates in particular to a polymer composition comprising an elastomer and a crystalline polymer, such as a polypropylene homopolymer or a polypropylene/alpha-olefin copolymer. More particularly, this invention relates to a polymer composition wherein the elastomeric component has a hardness (shore a) of 85 or less. Furthermore, this document describes a polymer-based article for footwear and heels which requires an abrasion resistance preferably greater than 50% compared to the ungrafted polymer. The polymers described in this document are produced by a solution polymerization process carried out at between 20 and 250 ℃ using a geometrically constrained catalyst. The polymer is preferably grafted in the presence of a free radical initiator.

Nevertheless, there is a great interest in developing compositions with low compression set values for a range of articles and applications, and furthermore, in particular in developing materials with low compression set values at low temperatures. Generally, to improve the compression set of articles based on ethylene copolymers, a greater percentage of the ethylene copolymer having from 6 to 12 carbon atoms is added before polymerizationOf alpha-olefin comonomer units. However, low density plastomers having a high percentage of comonomer units having from 6 to 12 carbon atoms (such as ethylene copolymers) are sticky, which makes pelletization and material handling difficult. Furthermore, the removal of unreacted comonomer takes time and energy. Comonomers such as 1-octene are also more expensive than ethylene. It is therefore economically advantageous to have as little C as possible in the ethylene copolymer-based articles₆–C₁₂Alpha-olefin comonomers to produce an amorphous structure.

Surprisingly, the inventors have found that the above problems can be solved by using a polymer composition comprising a specific ethylene copolymer, which requires less comonomer to provide an exemplary compression set value at-25 ℃.

In addition, the polymer compositions exhibit a range of other advantageous properties, such as high toughness, very low levels of extractables, and excellent compatibility with other polymers and elastomers.

Disclosure of Invention

Accordingly, the present invention relates to an article comprising:

a polymer composition comprising a blend of a polymer and a metal,

wherein the polymer composition is obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups,

and

wherein the polymer composition has comonomer units comprising hydrolysable silane groups in an amount of greater than 0.5 wt%, based on the total weight of monomer units in the polymer composition,

wherein the ethylene copolymer comprises alpha-olefin comonomer units having from 6 to 12 carbon atoms,

and

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-per 100,000 CH_nTotal unsaturation of 20 to 100 unsaturated bonds of the group.

It has been surprisingly found that such articles comprising the polymer composition have a very low compression set at low temperatures, such as-25 ℃.

In another aspect, the present invention relates to an article consisting of:

a polymer composition comprising a blend of a polymer and a metal,

wherein the polymer composition is obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups,

and

wherein the polymer composition has comonomer units comprising hydrolysable silane groups in an amount of greater than 0.5 wt%, based on the total weight of monomer units in the polymer composition,

wherein the ethylene copolymer comprises alpha-olefin comonomer units having from 6 to 12 carbon atoms,

and

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-per 100,000 CH_nTotal unsaturation of 20 to 100 unsaturated bonds of the group.

In yet another aspect, the present invention relates to a method for producing an article, the method comprising the steps of:

a) there is provided an ethylene copolymer having a high molecular weight,

wherein the ethylene copolymer comprises alpha-olefin comonomer units having from 6 to 12 carbon atoms,

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-per 100,000 CH_nThe total degree of unsaturation of the groups 20 to 100 unsaturated bonds,

b) obtaining a polymer composition by grafting a comonomer unit comprising hydrolysable silane groups to an ethylene copolymer with a grafting agent such as VTMS to obtain a polymer composition having 0.5 to 10 wt% of a comonomer unit comprising hydrolysable silane groups,

c) blending the silane-grafted polymer composition from step b) with a silanol condensation catalyst,

d) forming the composition from step c) into an article.

Furthermore, the present invention relates to an article obtainable by the above-described process.

In another aspect, the invention relates to the use of a polymer composition for reducing the permanent set (compression set measured according to ISO 815-1: 2010-9) of a crosslinked article compared to a crosslinked article obtainable from an ethylene copolymer having a lower total degree of unsaturation:

wherein the polymer composition is obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups,

and

wherein the polymer composition has comonomer units comprising hydrolysable silane groups in an amount of greater than 0.5 wt%, based on the total weight of monomer units in the polymer composition,

wherein the ethylene copolymer comprises alpha-olefin comonomer units having from 6 to 12 carbon atoms,

and

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-per 100,000 CH_nTotal unsaturation of 20 to 100 unsaturated bonds of the group.

Definition of

Where an indefinite or definite article is used, when referring to a singular noun e.g. "a", "an" or "the", this includes a plural of that noun unless something else is specifically stated.

Copolymers are polymers formed by the reaction of two or more different monomers (forming more than one type of monomer unit).

Plastomers are polymers that combine the properties of elastomers and plastics, such as rubber-like properties with the processability of plastics.

Ethylene-based plastomers are plastomers having a predominant molar amount of ethylene monomer units.

EthyleneRadical groups are used to refer to unsaturated groups at the ends of the hydrocarbon polymer chain. The vinyl group being represented by the formula R-CH ═ CH₂And (4) defining.

Flash evaporation is used to refer to lowering the pressure in the reaction vessel to cause the liquid components to evaporate, often leaving a solid product behind. Due to the reduced pressure, evaporation occurs rapidly and the liquid "flashes" into a vapor.

VTMS refers to vinyltrimethoxysilane as a silane grafting agent.

By crosslinked is meant that the polymer chains are optionally crosslinked via comonomer units present in the polymer composition comprising hydrolysable silane groups. The optional crosslinking is generally carried out in the presence of a silanol condensation catalyst. Thus, during the optional crosslinking step, the units comprising hydrolysable silane groups present in the polymer composition hydrolyse under the influence of water in the presence of a silanol condensation catalyst. This hydrolysis step results in the loss of alcohol groups and the formation of silanol groups, which crosslink in a subsequent condensation reaction, wherein water is lost and Si-O-Si chains are formed between other hydrolysable silane groups present in the polymer composition. Silane crosslinking techniques are known and described in, for example, US 4,413,066, US 4.297,310, US 4,351,876, US 4,397,981, US 4,446,283 and US 4,456,704. The crosslinked polymer composition has a typical network structure, i.e., interpolymer crosslinks (bridges), as is well known in the art.

Hereinafter, amounts are given in% (wt%) by weight unless otherwise indicated.

Hereinafter, various embodiments of the present invention are defined in more detail.

Ethylene copolymers

Ethylene copolymer refers to a starting ethylene copolymer that is blended to form a polymer composition, i.e., prior to grafting the polymer composition with comonomer units comprising hydrolyzable silane groups, described in more detail below.

The ethylene copolymers comprise alpha-olefin comonomer units having from 6 to 12 carbon atoms. Suitably, the ethylene copolymer comprises from 10 to 50 wt% of alpha olefin comonomer units having from 6 to 12 carbon atoms, preferably from 20 to 45 wt% of alpha olefin comonomer units having from 6 to 12 carbon atoms and most preferably from 30 to 40 wt% of alpha olefin comonomer units having from 6 to 12 carbon atoms. The alpha olefin comonomer units are preferably linear alpha olefin comonomer units.

The alpha olefin comonomer units are preferably selected from 1-octene and/or 1-hexene, most preferably the alpha olefin comonomer units are 1-octene. Preferably, copolymers of ethylene and 1-octene are used in the articles of the invention. In certain additional embodiments, the ethylene copolymer has a 1-octene content of 10 to 60 wt%, preferably 10 to 50 wt%, more preferably 20 to 40 wt% or 20 to 38 wt%. The 1-octene content can be measured by using NMR to determine C in the polymer chain₈The ratio of the monomers.

The ethylene copolymer has a weight ratio of 840 to 890kg/m³Preferably 850 to 880kg/m³Most preferably 860 to 870kg/m³A density within the range of (1).

Preferably, the ethylene copolymer has a crystallinity of between 2% and 9%, more preferably between 5% and 8%, such as between 6.5% and 7.5%, such as about 7%, measured according to the method described below.

The ethylene copolymer has 100,000 CH groups per molecule_nThe radical having from 20 to 100 unsaturated bonds, preferably per 100,000 CH_nThe group having 30 to 80 unsaturated bonds, more preferably per 100,000 CH_nA total unsaturation level of 40 to 60 unsaturated bonds in the group. Without being bound by any theory, it is believed that the higher unsaturation causes the polymer to better resist deformation at low temperatures.

Preferably, the ethylene copolymer has a ratio of vinyl groups to the total amount of unsaturated groups in the ethylene copolymer prior to grafting with the comonomer comprising hydrolysable silane groups of less than 0.6 and more preferably from 0.3 to 0.1. The ratio of the total amount of vinyl groups to unsaturated groups in the ethylene copolymer can be calculated using equation (I):

preferably, the ethylene copolymer has a cis group to trans group ratio of greater than 1 and more preferably greater than 2.

Further, the ethylene copolymer preferably has a Tg of-40 ℃ to-80 ℃, more preferably-50 ℃ to-70 ℃.

The ethylene copolymer may have an MFR in the range of 0.01 to 5.0g/10min, preferably in the range of 0.25 to 1.25g/10min, more preferably in the range of 0.25 to 1.20g/10min₂(ISO 1133；190℃；2.16kg)。

Suitable ethylene copolymers may be any copolymer of ethylene with an alpha olefin having from 6 to 12 carbon atoms, the alpha olefin having the properties described above. Preferably, the ethylene copolymer is selected from ethylene-based plastomers. Suitable ethylene-based plastomers are commercially available, i.e., from Borealis under the trade name Queo.

In certain such embodiments, the ethylene copolymer may be produced in a solution polymerization process comprising the steps of:

a) the ethylene monomer unit is provided and the ethylene monomer unit,

b) providing alpha olefin comonomer units having from 6 to 12 carbon atoms,

c) providing a liquid hydrocarbon solvent, wherein the liquid hydrocarbon solvent,

d) there is provided a metallocene catalyst which is capable of,

e) heating the reaction vessel above the melting point of the ethylene copolymer to allow the polymerization process to proceed, thereby obtaining the ethylene copolymer in solution,

f) the solution is flashed to separate the polymer from unreacted monomer and solvent,

g) an ethylene copolymer was obtained.

The alpha-olefin comonomer units in step b) are preferably 1-octene. Preferably, the 1-octene content is from 10 to 45 wt% of the total ethylene copolymer obtained in step g.

Alternatively, these ethylene-based plastomers may be prepared by known methods, such as one-stage or two-stage polymerization methods, including solution polymerization, slurry polymerization, gas phase polymerization, or combinations thereof, in the presence of suitable catalysts known to those skilled in the art, such as vanadium oxide catalysts or single site catalysts, e.g., metallocene catalysts or constrained geometry catalysts.

Preferably, these ethylene-based plastomers are prepared by a one-stage or two-stage solution polymerization process (in particular by a high temperature solution polymerization process at temperatures above 100 ℃) in the presence of a metallocene catalyst.

This process is essentially based on polymerizing the monomers and suitable comonomers in a liquid hydrocarbon solvent in which the resulting polymer is soluble. The polymerization is carried out at a temperature higher than the melting point of the polymer, thereby obtaining a polymer solution. The solution is flashed to separate the polymer from unreacted monomer and solvent. The solvent is then recovered and recycled in the process.

Preferably, the solution polymerization process is a high temperature solution polymerization process using a polymerization temperature above 100 ℃. Preferably, the polymerization temperature is at least 110 ℃, more preferably at least 150 ℃. The polymerization temperature may be up to 250 ℃.

The pressure in this solution polymerization process is preferably in the range of from 10 bar to 100 bar, preferably from 15 bar to 100 bar and more preferably from 20 bar to 100 bar.

The liquid hydrocarbon solvent used is preferably a hydrocarbon having 5 to 12 carbon atoms, which may be unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha. More preferably, an unsubstituted hydrocarbon solvent having 6 to 10 carbon atoms is used.

Polymer composition

The polymer composition may be obtained by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups. The amount of the comonomer units comprising hydrolysable silane groups in the polymer composition is more than 0.5 wt%, preferably the amount of the comonomer units comprising hydrolysable silane groups is at least 0.75 wt%, more preferably at least 1.5 wt%, based on the total weight of the monomer units in the ethylene copolymer. Generally, the amount of comonomer units including hydrolysable silane groups is no more than 10 wt%, preferably no more than 7.5 wt%, more preferably no more than 5.0 wt%, most preferably no more than 3.5 wt%, based on the total weight of monomer units in the polymer composition. Most preferably, the polymer composition comprises 1.5 to 3.5 wt% of comonomer units comprising hydrolysable silane groups, based on the total amount of monomer units in the ethylene copolymer.

The polymer composition may also comprise additional comonomer units comprising hydrolysable silane groups.

The comonomer unit comprising a hydrolysable silane group is a comonomer unit containing a hydrolysable silane group, which is used to copolymerize the silane group containing units. The comonomer units are preferably unsaturated silane compounds or preferably comonomer units of the formula (II)

R¹SiR² _qY_3-q (II)

Wherein

R¹Is an ethylenically unsaturated hydrocarbyl, hydrocarbyloxy or (meth) acryloyloxyalkyl group,

each R²Independently an aliphatic saturated hydrocarbon group,

y, which may be identical or different, is a hydrolyzable organic radical, and

q is 0, 1 or 2.

Specific examples of unsaturated silane compounds are these compounds: wherein R is¹Is vinyl, allyl, isopropenyl, butenyl, cyclohexyl or gamma- (meth) acryloxypropyl; y is methoxy, ethoxy, formyloxy, acetoxy, propionyloxy or an alkyl or arylamino group; and, R²(if present) is a methyl, ethyl, propyl, decyl or phenyl group.

Further suitable silane compounds or preferred comonomers are, for example, gamma- (meth) acryloxypropyltrimethoxysilane, gamma- (meth) acryloxypropyltriethoxysilane and vinyltriacetoxysilane or combinations of two or more thereof.

As a preferred subgroup, the units of the formula (II) are unsaturated silane compounds, or preferably comonomers of the formula (III),

CH₂＝CHSi(OA)₃ (III)

wherein each a is independently a hydrocarbyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.

Preferred comonomers/compounds of formula (III) are vinyltrimethoxysilane, vinyldimethoxyethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane being most preferred.

In certain embodiments, the ethylene copolymer has a molecular weight of 840 to 890kg/m after grafting with comonomer units comprising hydrolyzable silane groups³Preferably 850 to 880kg/m³Most preferably 860 to 870kg/m³A density within the range of (1).

The polymer composition may further comprise one or more additives selected from the group comprising slip agents, antiblock agents, UV stabilizers, acid scavengers, antioxidants, alpha-and/or beta-nucleating agents, antistatic agents, and the like, and mixtures thereof, in a total amount of from 0.0 to 5.0 weight percent, based on the total weight of the composition. Such additives are well known in the art.

The slip agent migrates to the surface and acts as a lubricant between the polymer and between the polymer and the metal roller, thereby reducing the coefficient of friction (CoF). Examples are fatty acid amides such as erucamide (CAS number 112-84-5), oleamide (CAS number 301-02-0) or stearamide (CAS number 124-26-5).

An example of an antioxidant commonly used in the art is a sterically hindered phenol (such as CAS number 6683-19-8, also by BASF as Irganox 1010 FF)^TMSold), phosphorus based antioxidants (such as CAS number 31570-04-4, also by Clariant as Hostanox PAR 24(FF)^TMSold as Irgafos 168(FF) TM by BASF), sulfur-based antioxidants (such as CAS number 693-36-7, as Irganox PS-802FL by BASF^TMSold), a nitrogen-based antioxidant such as 4,4 '-bis (1, 1' -dimethylbenzyl) diphenylamine, or an antioxidant blend.

Acid scavengers are also well known in the art. Examples are calcium stearate, sodium stearate, zinc stearate, oxides of magnesium and zinc, synthetic hydrotalcite (e.g. SHT, CAS No. 11097-59-9), lactate esters and lactates, as well as calcium stearate (CAS No. 1592-23-0) and zinc stearate (CAS No. 557-05-1).

Common anti-caking agents are: natural silicas, such as diatomaceous earth (such as CAS number 60676-86-0 (SuperfFloss)^TM) CAS number 60676-86-0(Superfloss E)^TM) Or CAS number 60676-86-0(Celite 499)^TM) Synthetic silica (such as CAS No. 7631-86-9, CAS No. 112926-00-8, CAS No. 7631-86-9, or CAS No. 7631-86-9), silicate (such as aluminum silicate (kaolin) CAS No. 1318-74-7, sodium aluminosilicate CAS No. 1344-00-9, calcined kaolin CAS No. 92704-41-1, aluminum silicate CAS No. 1327-36-2, or calcium silicate CAS No. 1344-95-2), synthetic zeolite (such as calcium aluminosilicate hydrate CAS No. 1344-01-0, or calcium aluminosilicate hydrate CAS No. 1344-01-0).

Suitable UV stabilizers are: for example, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate (CAS number 52829-07-9, Tinuvin 770); 2-hydroxy-4-n-octyloxy-benzophenone (CAS number 1843-05-6, Chimassorb 81).

The alpha nucleating agent may be sodium benzoate (CAS number 532-32-1), 1,3:2, 4-bis (3, 4-dimethylbenzylidene) sorbitol (CAS number 135861-56-2, Millad 3988).

Suitable antistatic agents are, for example, glycerol esters (CAS number 97593-29-8) or ethoxylated amines (CAS number 71786-60-2 or 61791-31-9) or ethoxylated amides (CAS number 204-393-1).

Typically, these additives are added in amounts of 100 to 2.000ppm for each individual component of the polymer.

Preferably, the optional additives are added during the polymerization process of the ethylene copolymer, or during subsequent grafting of the ethylene copolymer with comonomer units comprising hydrolysable silane groups, or during blending of the polymer composition with a silanol condensation catalyst.

The optional additives may be added to the ethylene copolymer in the form of a masterbatch in which one or more additives are blended with the carrier polymer in concentrated amounts. Any optional carrier polymer is calculated as the total amount of additives based on the amount of the total polyethylene composition.

The polymer composition of the present invention may also include a filler, which is different from the additive depending on the article. Typically, the amount of filler is higher than the amount of additive described above. As non-limiting examples of fillers, Flame Retardants (FR), carbon black and titanium oxide can be mentioned. As examples of the flame retardant as the filler, for example, magnesium hydroxide and ammonium polyphosphate may be mentioned. Preferably, the optional filler is selected from one or more of the group of magnesium hydroxide, ammonium polyphosphate, titanium oxide and carbon black. As will be apparent to the skilled person, the amount of filler will generally depend on the nature of the filler and the desired end use. Such fillers are generally commercially available and are described, for example, in "plastics Additives Handbook", 5 th edition, 2001, of Hans Zweifel. Further, the above-mentioned additives and fillers are not included in the definition of the Silane Condensation Catalyst (SCC).

The polymer composition preferably comprises the ethylene copolymer in an amount of from 30 to 99.9 wt. -%, preferably from 40 to 99.0 wt. -%, still more preferably from 50 to 98.5 wt. -%, based on the total weight of the composition.

In one embodiment, the ethylene copolymer is the only polymer component of the polymer composition. In this embodiment, the ethylene copolymer is preferably present in an amount of 94 to 99.9 wt%, more preferably 95 to 99.5 wt%, and most preferably 96 to 98.5 wt% of the polymer composition, based on the total weight of the composition.

In another embodiment, the polymer composition may include additional polymer components. These polymer components are preferably selected from ethylene homo-or copolymers (such as LDPE, LLDPE, UHDPE or HDPE) and propylene homo-or copolymers, such as propylene homo-, random-or heterophasic propylene copolymers. These additional polymer components may be added to the polymer composition before, during or after the grafting step.

The additional polymer component may be present in the polymer composition in an amount of from 30 to 80 wt. -%, preferably from 40 to 75 wt. -%, and most preferably from 50 to 70 wt. -%, based on the total amount of the polymer composition.

In this embodiment, the ethylene copolymer is preferably present in an amount of from 20 to 70 wt%, preferably from 25 to 60 wt% and most preferably from 30 to 50 wt%, based on the total weight of the composition.

The melting point (measured according to the method described below) of the polymer composition according to the invention is optionally below 130 ℃, preferably below 120 ℃, more preferably below 110 ℃ and most preferably below 100 ℃.

Article of manufacture

The present invention relates to an article comprising a polymer composition of the invention as defined above or below. The polymer composition is preferably crosslinked after formation of the article by hydrolysis of the silane groups in the presence of a silanol condensation catalyst.

The Silanol Condensation Catalyst (SCC), if present, is preferably selected from the group of: carboxylates of metals (such as tin, zinc, iron, lead and cobalt); titanium compounds bearing groups hydrolysable to bronsted acids (preferably as described in european application No. ep 10166636.0) or aromatic organic acids such as aromatic organic sulphonic acids. The silanol condensation catalyst, if present, is more preferably selected from DBTL (dibutyltin dilaurate), DOTL (dioctyltin dilaurate), especially DOTL; the above titanium compound having a group hydrolyzable to a Bronsted acid; or an aromatic organic sulfonic acid having a meaning well known in the art.

Preferably, the silanol condensation catalyst may be a sulfonic acid, preferably an aromatic organic sulfonic acid, which is an organic sulfonic acid comprising a structural element according to formula (IV):

Ar(SO₃H)x (IV)

wherein Ar is an aryl group which may be substituted or unsubstituted, and if substituted, suitably has at least one hydrocarbyl group comprising up to 50 carbon atoms, and wherein x is at least 1;

alternatively, the structural element is a precursor of a sulphonic acid of formula (IV) comprising an anhydride of a sulphonic acid of formula (IV) or a sulphonic acid of formula (IV) which has been provided with a hydrolysable protecting group, such as an acetyl group which can be removed by hydrolysis.

The silanol condensation catalyst is preferably present in the polymer composition in an amount of from 0.0001 to 1.0 wt. -%, more preferably from 0.01 to 0.75 wt. -%, most preferably from 0.1 to 0.5 wt. -%, based on the total weight of the polymer composition.

The degree of crosslinking of the polymer composition after crosslinking is preferably in the range of 75% to 99%, more preferably 90% to 99%.

Compression set is a measure of how much a material is permanently deformed after a predetermined period of time of application of pressure; thus, compression set is a useful indicator of the resistance of a material to permanent deformation under a particular set of conditions. Without being bound by any theory, it is believed that a high degree of Si-grafting, preferably a degree of crosslinking of more than 90%, is required for good elasticity of the polymer composition, and this leads to low compression set values at low temperatures. This is also reflected in the gel content of the composition, which increases when the amount of comonomer comprising hydrolysable silane groups is increased.

Preferably, the article has a compression set after crosslinking of from 0% to 5%, preferably from 0% to 4%, more preferably from 0% to 3%, when measured at-25 ℃. Without being bound by any theory, it is believed that the very low, almost negligible crystallinity (in the range of 6% to 7%) of the ethylene copolymers according to the invention (such as, for example, Queo from Borealis) makes the articles produced from the ethylene copolymers very elastic even at low temperatures where all chains capable of crystallization will crystallize. Furthermore, without being bound by any theory, it is believed that the high level of unsaturation of the ethylene copolymers according to the present invention contributes here to the surprisingly low compression set values obtained at low temperatures.

After crosslinking, the article preferably has a compression set of from 0% to 20%, preferably from 0% to 15%, most preferably from 0% to 12.5%, when measured at 23 ℃. It is generally preferred that the article has a low compression set at elevated temperatures such as 23 ℃, or 30 ℃, or 50 ℃, or 70 ℃, or 90 ℃ and a low compression set at low temperatures such as-25 ℃, or-10 ℃, or-5 ℃.

The article is preferably formed by extrusion, injection molding, blow molding or compression molding, most preferably the article is an extruded article.

A non-limiting list of uses for articles according to the invention includes weather stripping, automotive parts such as sealing systems for doors, trunks and hoods, shoe soles and other articles where low deformation is required at low temperatures.

In certain embodiments, the present invention relates to the use of a polymer composition for reducing the permanent set (compression set measured according to ISO 815-1: 2010-9) of a crosslinked article compared to a crosslinked article obtainable from an ethylene copolymer having a lower total degree of unsaturation:

wherein the polymer composition is obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups,

and

wherein the polymer composition has comonomer units comprising hydrolysable silane groups in an amount of greater than 0.5 wt%, based on the total weight of monomer units in the polymer composition,

wherein the ethylene copolymer comprises alpha-olefin comonomer units having from 6 to 12 carbon atoms,

and

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-per 100,000 CH_nTotal unsaturation of 20 to 100 unsaturated bonds of the group.

In certain embodiments, the present invention relates to the use of a polymer composition for reducing the permanent set (compression set measured according to ISO 815-1: 2010-9) of a crosslinked article compared to a crosslinked article comprising an ethylene copolymer having a lower total degree of unsaturation:

wherein the polymer composition is obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups,

and

wherein the polymer composition has comonomer units comprising hydrolysable silane groups in an amount of greater than 0.5 wt%, based on the total weight of monomer units in the polymer composition,

and

wherein the polymer composition comprises at least 90% of an ethylene copolymer,

wherein the ethylene copolymer comprises alpha-olefin comonomer units having from 6 to 12 carbon atoms,

and

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-per 100,000 CH_nTotal unsaturation of 20 to 100 unsaturated bonds of the group.

Method

The invention also relates to a method for producing an article, comprising the steps of:

a) there is provided an ethylene copolymer having a high molecular weight,

wherein the ethylene copolymer comprises alpha-olefin comonomer units having from 6 to 12 carbon atoms,

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-per 100,000 CH_nThe total degree of unsaturation of the groups 20 to 100 unsaturated bonds,

b) obtaining a polymer composition by grafting a comonomer unit comprising hydrolysable silane groups to an ethylene copolymer with a grafting agent such as VTMS to obtain a polymer composition having 0.5 to 10 wt% of a comonomer unit comprising hydrolysable silane groups,

c) blending the silane-grafted polymer composition from step b) with a silanol condensation catalyst,

d) forming the composition from step c) into an article.

Preferably, the article is crosslinked in the presence of water to obtain a gel content of 75% to 99%, preferably 90% to 99%. The crosslinking step may be carried out at room temperature (25 ℃), or at elevated temperatures such as 40 ℃, or 50 ℃, or above 60 ℃.

In step (d), the article may be formed by extrusion, injection molding, blow molding or compression molding.

In a preferred aspect, the process according to the invention comprises using a silanol condensation catalyst in step (c), wherein the silanol condensation catalyst may be a sulphonic acid, preferably wherein the silanol condensation catalyst is an aromatic organic sulphonic acid which is an organic sulphonic acid and comprises the following structural elements:

Ar(SO₃H)_x (IV)

wherein Ar is a substituted or unsubstituted aryl group and, if substituted, suitably has at least one hydrocarbyl group comprising up to 50 carbon atoms, and wherein x is at least 1;

or precursors wherein the structural element is a sulphonic acid of formula (IV) comprising an anhydride of a sulphonic acid of formula (IV) or a sulphonic acid of formula (IV) which has been provided with a hydrolysable protecting group, for example an acetyl group which can be removed by hydrolysis.

The invention also relates to an article obtainable by the above process.

Detailed description of the invention

In a first particularly preferred embodiment, the present invention relates to an article comprising:

a polymer composition comprising a blend of a polymer and a metal,

wherein the polymer composition is obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups,

and

wherein the polymer composition has comonomer units comprising hydrolysable silane groups in an amount of greater than 0.5 wt%, based on the total weight of monomer units in the polymer composition,

wherein the ethylene copolymer comprises 1-octene units,

and

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-per 100,000 CH_nTotal unsaturation of 20 to 100 unsaturated bonds of the group, and

wherein the ethylene copolymer comprises 30 to 40 wt% of 1-octene units (as determined using NMR), based on the total amount of monomer units in the ethylene copolymer, and

wherein the article has a compression set after crosslinking of from 0% to 5% when measured at-25 ℃ (ISO 815-1:2010-9 at-25 ℃).

In a second preferred embodiment, the present invention relates to an article comprising:

a polymer composition comprising a blend of a polymer and a metal,

wherein the polymer composition is obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups,

and

wherein the polymer composition has comonomer units comprising hydrolysable silane groups in an amount of greater than 0.5 wt%, based on the total weight of monomer units in the polymer composition,

wherein the ethylene copolymer comprises 1-octene units,

and

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-per 100,000 CH_nTotal unsaturation of 20 to 100 unsaturated bonds of the group, and

wherein the ethylene copolymer comprises 30 to 40 wt% of 1-octene units (as determined using NMR), based on the total amount of monomer units in the ethylene copolymer, and

wherein the ratio of vinyl groups to total unsaturated groups in the ethylene polymer is from 0.3 to 0.1.

In a third preferred embodiment, the present invention is directed to an article comprising:

a polymer composition comprising a blend of a polymer and a metal,

wherein the polymer composition is obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups,

and

wherein the polymer composition has comonomer units comprising hydrolysable silane groups in an amount of greater than 0.5 wt%, based on the total weight of monomer units in the polymer composition,

wherein the ethylene copolymer comprises 1-octene units,

and

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-per 100,000 CH_nTotal unsaturation of 20 to 100 unsaturated bonds of the group, and

wherein the ethylene copolymer comprises 30 to 40 wt% of 1-octene units (as determined using NMR), based on the total amount of monomer units in the ethylene copolymer, and

wherein the ethylene copolymer has a ratio of cis groups to trans groups of greater than 2.

In a fourth preferred embodiment, the present invention relates to an article comprising:

a polymer composition comprising a blend of a polymer and a metal,

wherein the polymer composition is obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups,

and

wherein the polymer composition has comonomer units comprising hydrolysable silane groups in an amount of greater than 0.5 wt%, based on the total weight of monomer units in the polymer composition,

wherein the ethylene copolymer comprises alpha-olefin comonomer units having from 6 to 12 carbon atoms,

and

wherein the ethylene copolymer is characterized by having:

-840 to 890kg/m³The density of (a) of (b),

-per 100,000 CH_nRadical 20 toThe total degree of unsaturation of 100 unsaturated bonds,

-a crystallinity between 5% and 8% as measured by DSC using a cooling and heating rate of 10 ℃/min, and

wherein the ethylene copolymer comprises 30 to 40 wt% of 1-octene units (as determined using NMR), based on the total amount of monomer units in the ethylene copolymer, and

wherein the article has a compression set after crosslinking of from 0% to 5% when measured at-25 ℃ (ISO 815-1:2010-9 at-25 ℃).

The above embodiments may be combined with any of the preferred features herein as appropriate.

Drawings

FIG. 1: corresponding to example 1, the weight% VTMS in the polymer composition correlates with the% compression set over a range of temperatures (values are shown in table 4).

FIG. 2: comparison of the compression set properties of two different base resins at temperatures from-23 ℃ to 100 ℃ corresponding to example 2 (values are shown in table 5).

Detailed Description

Examples section

The following examples are included to illustrate certain aspects and embodiments of the invention described in the claims. However, those skilled in the art will appreciate that the following description is illustrative only and should not be taken in any way as a limitation of the present invention.

Measurement method

a) Melt flow rate: the melt flow rate MFR of ethylene homo-and copolymers was measured according to ISO 1133 at 190 ℃ and under a load of 2.16kg₂。

b) The density was measured according to ISO 1183-. Sample preparation was performed by compression molding according to ISO 1872-2: 2007.

c) Quantitative Nuclear Magnetic Resonance (NMR) spectroscopy:

content of polar comonomer present in the polymer (wt% and mol%):

quantitative Nuclear Magnetic Resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymer in the polymer composition.

Quantitative recording in solution state using a Bruker Advance III 400NMR spectrometer operating at 400.15MHz¹H NMR spectrum. All spectra were recorded at 100 ℃ using a standard broadband inverted 5mm probe using nitrogen for all pneumatics. Approximately 200mg of the material was dissolved in 1, 2-tetrachloroethane-d using di-tert-Butylhydroxytoluene (BHT) (CAS 128-37-0) as a stabilizer₂(TCE-d₂) In (1). A standard single pulse excitation was used with a 30 degree pulse, a relaxation delay of 3s and no sample rotation. A total of 16 transient signals were acquired per spectrum using 2 virtual scans. With a residence time of 60 μ s, a total of 32k data points were collected per FID, which corresponds to a spectral window of about 20 ppm. The FID is then zero-padded to 64k data points and an exponential window function of 0.3Hz line broadening is used. This setup was chosen primarily to be able to resolve the quantitative signal resulting from the copolymerization of vinyltrimethylsiloxane when present in the same polymer.

Quantification using a custom spectral analysis automation program¹H NMR spectra were processed, integrated and quantitative property measurements. All chemical shifts are internally referenced to the residual protonated solvent signal at 5.95 ppm.

When present, in various comonomer sequences, characteristic signals resulting from the incorporation of Vinyl Acetate (VA), Methyl Acrylate (MA), Butyl Acrylate (BA) and Vinyl Trimethicone (VTMS) were observed (see J Randall). All comonomer contents are calculated relative to all other monomers present in the polymer.

Ethylene comonomer content was quantified using integral of bulk (bulk) aliphatic (bulk) signal between 0.00 and 3.00 ppm. This integral may include 1VA (3) and α VA (2) sites from isolated vinyl acetate incorporation, MA and α MA sites from isolated methyl acrylate incorporation, 1BA (3), 2BA (2), 3BA (2), "BA (1) and α BA (2) sites from isolated butyl acrylate incorporation, VTMS and α VTMS sites from isolated vinyl silane incorporation and aliphatic sites from BHT and sites from polyethylene sequences. The total ethylene comonomer content was calculated based on bulk integration and compensation for the observed comonomer sequence and BHT:

E＝(1/4)*[I_body-5*VA-3*MA-10*BA-3*VTMS-21*BHT]

It should be noted that half of the alpha signal in the bulk signal represents ethylene rather than comonomer and introduces insignificant error due to the inability to compensate for the two saturated chain ends (S) without the associated branching sites.

d) Quantification of comonomer (C8) content of Poly (ethylene-co-1-octene) copolymer

Use to¹H and¹³c Bruker Avance III 500NMR spectrometers operating at 500.13 and 125.76MHz respectively to record quantitative measurements in the molten state¹³C{¹H } NMR spectrum. For all pneumatic devices, nitrogen was used¹³C-optimized 7mm Magic Angle Spinning (MAS) probes recorded all spectra at 150 ℃. Approximately 200mg of material was loaded into a 7mm outer diameter zirconia MAS rotor and rotated at 4 kHz. This setting was chosen primarily for the high sensitivity required for rapid identification and accurate quantification klimkike 01, parkinson02, cartignoles 03, NMR 04. Standard single pulse excitation was used with transient NOE { pollard05, klimke01} and RS-HEPT decoupling scheme { Filif06, Griffin07} at 3s short cycle delay. A total of 1024(1k) transient signals were collected per spectrum. This setup was chosen primarily due to its high sensitivity to low comonomer content.

Quantification using a custom spectral analysis automation program¹³C{¹H NMR spectra were processed, integrated and quantitative property measurements. All chemical shifts are internally referenced to the bulk methylene signal (δ +) at 30.00ppm { Randall08 }.

Characteristic signals corresponding to the incorporation of 1-octene { Randall08, Liu09, Qiu10, Busisco11, Zhou12} were observed and all comonomer contents were calculated relative to all other monomers present in the polymer.

Characteristic signals resulting from isolated 1-octene incorporation (i.e., EEOEE comonomer sequence) were observed. Isolated 1-octene incorporation was quantified using integration of the signal at 38.32 ppm. The integrals were assigned to the unresolved signals corresponding to the a B6 and a B6B6 sites of the isolated (EEOEE) and isolated double-discontinuous (EEOEE) 1-octene sequences, respectively. Integration of β β B6B6 sites at 24.7ppm was used to compensate for the effect of two β B6B6 sites:

O＝I_*B6+*βB6B6-2*I_ββB6B6

characteristic signals resulting from continuous 1-octene incorporation (i.e., EEOOEE comonomer sequence) were also observed. This continuous 1-octene incorporation was quantified taking into account the number of reporting sites per comonomer using the integral of the signal at 40.48ppm assigned to α α B6B6 site:

OO＝2*I_ααB6B6

characteristic signals resulting from isolated discontinuous 1-octene incorporation (i.e., eeoeoeoe comonomer sequence) were also observed. This isolated discontinuous 1-octene incorporation was quantified taking into account the number of reporter sites per comonomer using the integral of the signal at 24.7ppm assigned to β β B6B6 site:

OEO＝2*I_ββB6B6

characteristic signals resulting from isolated three consecutive 1-octene incorporations (i.e., EEOOOEE comonomer sequences) were also observed. This isolated three-consecutive 1-octene incorporation was quantified taking into account the number of reporter sites per comonomer using the integral of the signal at 41.2ppm assigned to α α γ B6B6 site:

OOO＝3/2*I_ααγB6B6B6

in the case where no other signal indicative of other comonomer sequences was observed, the total 1-octene comonomer content was calculated based on the amount of isolated (EEOEE), isolated bicontinuous (EEOOEE), isolated discontinuous (EEOEOEE) and isolated trisequential (EEOOOEE) 1-octene comonomer sequences alone:

O_{general assembly}＝O+OO+OEO+OOO

Characteristic signals resulting from saturated end groups were observed. This saturated end group was quantified using the average integral of the two resolved signals at 22.84 and 32.23 ppm. The 22.84ppm integral was assigned to the unresolved signals of 2B6 and 2S sites corresponding to 1-octene and saturated chain ends, respectively. The 32.23ppm integral was assigned to the unresolved signals of 3B6 and 3S sites corresponding to 1-octene and saturated chain ends, respectively. The total 1-octene content was used to compensate for the effect of 2B6 and 3B 61-octene sites:

S＝(1/2)*(I_2S+2B6+I_3S+3B6-2*O_{general assembly})

The ethylene comonomer content was quantified using the integral of the bulk methylene (bulk) signal at 30.00 ppm. This integral includes the gamma and 4B6 sites and delta from 1-octene⁺A site. The total ethylene comonomer content was calculated based on bulk integration and compensation for observed 1-octene sequences and end groups:

E_{general assembly}＝(1/2)*[I_Body+2*O+1*OO+3*OEO+0*OOO+3*S]

It should be noted that since the number of unconsidered and overcorrected ethylene units is equal, there is no need to compensate for bulk integration due to the presence of isolated triple incorporation (EEOOOEE) 1-octene sequences.

The total mole fraction of 1-octene in the polymer was then calculated as:

fO＝(O_{general assembly}/(E_{General assembly}+O_{General assembly})

The total comonomer incorporation of 1-octene in weight percent calculated from the mole fraction in a standard manner:

o [ wt% ] ═ 100 (fO 112.21)/((fO 112.21) + ((1-fO) × 28.05))

Klimke01

Klimke,K.,Parkinson,M.,Piel,C.,Kaminsky,W.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2006；207:382.

Parkinson02

Parkinson,M.,Klimke,K.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2007；208:2128.

Castignolles03

Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer 50(2009)2373

NMR04

NMR Spectroscopy of Polymers:Innovative Strategies for Complex Macromolecules,Chapter24,401(2011)

Pollard05

Pollard,M.,Klimke,K.,Graf,R.,Spiess,H.W.,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004；37:813.

Filip06

Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239

Grifin07

Griffin,J.M.,Tripon,C.,Samoson,A.,Filip,C.,and Brown,S.P.,Mag.Res.in Chem.200745,S1,S198

Randall08

J.Randall,Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C29,201.

Liu09

Liu,W.,Rinaldi,P.,McIntosh,L.,Quirk,P.,Macromolecules 2001,34,4757

Qiu10

Qiu,X.,Redwine,D.,Gobbi,G.,Nuamthanom,A.,Rinaldi,P.,Macromolecules 2007,40,6879

Busico11

Busico,V.,Carbonniere,P.,Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28,1128

Zhou12

Zhou,Z.,Kuemmerle,R.,Qiu,X.,Redwine,D.,Cong,R.,Taha,A.,Baugh,D.Winniford,B.,J.Mag.Reson.187(2007)225

e) Quantification of VTMS content and derivatization properties of polymers using quantitative Nuclear Magnetic Resonance (NMR) spectroscopy

The VTMS content of the polymer was quantified using quantitative Nuclear Magnetic Resonance (NMR) spectroscopy.

Quantitative melt-state recordings using a Bruker Avance III 500NMR spectrometer operating at 500.13MHz¹H NMR spectrum. For all pneumatic devices, nitrogen was used¹³C-optimized 7mm Magic Angle Spinning (MAS) probes recorded all spectra at 150 ℃. Approximately 200mg of material was loaded into a 7mm outer diameter zirconia MAS rotor and rotated at 4 kHz. This setting was chosen primarily for the high sensitivity required for rapid identification and accurate quantification klimke06, parkinson07, castignoles 09. A standard single pulse excitation was used with a short cyclic delay of 2 s. A total of 128 transient signals were collected per spectrum.

Quantification using a custom spectral analysis automation program¹H NMR spectra were processed, integrated and quantitative property measurements. All chemical shifts are internally referenced to the polyethylene methylene signal at 1.33 ppm.

In a number of comonomer sequences, characteristic signals resulting from the grafting of vinyltrimethylsiloxane were observed. Vinyl trimethyl siloxane grafting was quantified taking into account the number of reported cores per comonomer using the integral of the signal at 3.52ppm assigned to the 1VTMS site { branddolini 01 }.

gVTMS＝I_1VTMS/9

The ethylene content (E) was quantified using a bulk aliphatic (bulk) signal between 0.00-3.00 ppm. This integral must be compensated for by: subtract 4 times of VTMS (2 methylene groups, 2VTMS and 3VTMS) and add one time of VTMS (VTMS lost 1 proton) total 3 times of VTMS.

E ═ 3 gVTMS/4

It should be noted that insignificant error is introduced due to the inability to compensate for saturated chain ends without an associated branching site.

The total mole fraction of vinyltrimethylsiloxane in the polymer was calculated as:

fVTMS＝gVTMS/(E+gVTMS)

the total comonomer incorporation of vinyltrimethylsiloxane in weight percent calculated from the mole fraction in the standard manner: cttms [ wt% ], [100 × (fVTMS 148.23) ]/[ (fVTMS 148.23) + ((1-fVTMS) × 28.05) ]

By the said¹H NMR grafted vinyl trimethicone in weight percent cVTMS [ wt.%]The quantitative determination is independent of the possible incorporation of additional alpha-co-olefins having an even number of carbon atoms (e.g.C 4, C6 or C8) in the polyethylene chain.

brandolini01

A.J.Brandolini,D.D.Hills,“NMR spectra of polymers and polymer additives”,Marcel Deker Inc.,2000

klimke06

Klimke,K.,Parkinson,M.,Piel,C.,Kaminsky,W.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2006；207:382.

parkinson07

Parkinson,M.,Klimke,K.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2007；208:2128.

castignolles09

Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer 50(2009)2373

It will be apparent to the skilled person that the above principles may be similarly adjusted to quantify the content of any further polar comonomer other than MA, BA and VA if within the definition of polar comonomer given in this application, and to quantify the content of any further silane group containing units other than VTMS by using the integration of the corresponding characteristic signals if within the definition of silane group containing units given in this application.

f) Quantitative Nuclear Magnetic Resonance (NMR) Spectroscopy to quantify the amount of unsaturated groups present in a Polymer composition

Quantitative recording in solution state using a Bruker Advance III 400NMR spectrometer operating at 400.15MHz¹H NMR spectrum. All pneumatic units were purged with nitrogen at 125 deg.C¹³C-optimized 10mm selective excitation probe records all spectra. Approximately 250mg of material was dissolved in 7, 2-tetrachloroethane using approximately 3mg of Hostanox 03(CAS 32509-66-3) as a stabilizer_-c/2(TCE_-c/2) In (1). A standard single pulse excitation was used with a 30 degree pulse, a relaxation delay of 10s and a sample rotation of 10 Hz. A total of 128 transient signals were acquired per spectrum using 4 virtual scans. This setup was chosen primarily for the high resolution required for unsaturation quantification and stability of the vinylidene group { he10a, busico05a }. All chemical shifts are indirectly referenced to TMS at 0.00ppm using the signal generated by residual protonated solvent at 5.95 ppm.

End fat was observedGroup of vinyl radicals (R-CH ═ CH)₂) And using two coupled non-equivalent terminal portions CH at 4.95, 4.98 and 5.00 and 5.05ppm₂The amount is quantified by integration of protons (Va and Vb), taking into account the number of reporter sites per functional group:

N_{vinyl radical}＝IVab/2

An internal vinylidene group (RR (C ═ CH) was observed₂) Presence of corresponding characteristic signal, and using two CH's at 4.74ppm₂Integration of protons (D), quantifying this quantity taking into account the number of reporter sites per functional group:

N_{vinylidene radical}＝ID/2

When a characteristic signal corresponding to the presence of an internal cis-ethenylene group (E-RCH ═ CHR) or related structure is observed, the amount is quantified taking into account the number of reporter sites per functional group, using the integral of the two CH protons (C) at 5.39 ppm:

N_{cis form}＝IC/2

When no characteristic signal corresponding to the presence of an internal cis-ethenylene group (E-RCH ═ CHR) or related structure is visibly observed, then these groups are not counted and the parameter N is not used_{Cis form}。

A characteristic signal corresponding to the presence of an internal trans-ethenylene group (Z-RCH ═ CHR) was observed and the amount was quantified taking into account the number of reporter sites per functional group using the integral of the two CH protons (T) at 5.45 ppm:

N_{trans form}＝IT/2

A characteristic signal corresponding to the presence of an internal trisubstituted-vinylene group (RCH ═ CRR) or related structure phase is observed and the amount is quantified taking into account the number of reporter sites per functional group, using the integral of the CH proton (tri) at 5.14 ppm:

N_III＝I_III

Hostanox 03 stabilizer was quantified using the integration of multiple peaks from aromatic protons (a) at 6.92, 6.91, 6.69 and 6.89ppm and taking into account the number of reporter sites per molecule:

H＝IA/4

although it can pass through¹H NMR spectroscopy was used to quantify the amount of unsaturation, which is typically determined relative to the total carbon atom content in polyolefins. This allows for the exchange of¹³The amount of other microstructures directly obtained by C NMR spectroscopy was directly compared.

The methyl signals from the stabilizer and the carbon atoms associated with the unsaturated functionality not included in this region are compensated, and the total amount of carbon atoms is calculated from the integral of the bulk aliphatic signal between 2.85 and-1.00 ppm:

NC_{general assembly}(I entity-42' H)/2+ 2N_{Vinyl radical}+2*N_{Vinylidene radical}+2*N_{Cis form}+2*N_{Trans form}+2*N_III

The content of unsaturated groups (U) is calculated as the number of unsaturated groups per thousand total carbons (kCHn) in the polymer:

U＝1000*N/NC_{general assembly}

The total amount of unsaturated groups is calculated as the sum of the individual unsaturated groups observed and is therefore also reported per thousand total carbons:

U_{general assembly}＝U_{Vinyl radical}+U_{Vinylidene radical}+U_{Cis form}+U_{Trans form}+U_III

The relative content (U) of a particular unsaturated group is reported as the fraction of the given unsaturated group relative to the total amount of unsaturated groups:

reference to the literature

J.Randall:

J.Randall et.al.Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C29,201.

he10a:

He,Y.,Qiu,X,and Zhou,Z.,Mag.Res.Chem.2010,48,537-542.

busico05a:

Busico,V.et.al.Macromolecules,2005,38(16),6988-6996B)Examples

g) Melting temperature and degree of crystallinity

The melting temperature Tm, crystallization temperature Tcr and crystallinity were measured on 5 to 10mg, typically 8. + -. 0.5mg samples using a Mettler TA820 Differential Scanning Calorimeter (DSC). The crystallization and melting curves were obtained during a cooling and heating scan of 50K/min between-70 ℃ and 170 ℃. The peaks of the endothermic curve and the exothermic curve were taken as the melting temperature and the crystallization temperature. The crystallinity was calculated by comparison with the heat of fusion of fully crystalline polyethylene (i.e., 290J/g).

h) Degree of crosslinking (gel content):

the degree of crosslinking was measured on the crosslinked material by decalin extraction (measured according to ASTM D2765-01, method A).

i) Compression set: compression set is a typical way to measure the elasticity of a material. Compression set was measured according to ISO 815-1: 2010-9. A panel of the material studied was compressed at 25% for 24 hours at the given temperature. Thereafter, the compression was removed and the material was allowed to relax at room temperature for 30 min. The height difference (set) was measured and was in%.

j) Glass transition temperature: tg was determined by dynamic mechanical analysis according to ISO 6721-7. Measurements were made in torsional mode on compression molded samples (40X 10X 1mm3) between-100 ℃ and +150 ℃ with a heating rate of 2 ℃/min and a frequency of 1 Hz.

k) Number average molecular weight (M)_n) Weight average molecular weight (M)_w) And Molecular Weight Distribution (MWD) is determined by Gel Permeation Chromatography (GPC) according to the following method:

the weight average molecular weight Mw and the molecular weight distribution (MWD ═ Mw/Mn, where Mn is the number average molecular weight and Mw is the weight average molecular weight) were measured by methods based on ISO 16014-1:2003 and ISO 16014-4: 2003. A Waters Alliance GPCV2000 instrument equipped with a refractive index detector and an in-line viscometer, using a 3 XTSK-gel column (GMHXL-HT) from TosoHaas and 1,2, 4-trichlorobenzene (TCB stabilized with 200mg/L of 2, 6-di-tert-butyl-4-methyl-phenol) as solvent, at 145 ℃ and a constant flow rate of 1mL/min, was used. 216.5. mu.L of sample solution was injected for each analysis. The column set was calibrated using a relative calibration with 19 narrow MWD Polystyrene (PS) standards in the range of 0.5kg/mol to 11500 kg/mol and a set of well characterized broad polypropylene standards. All samples were prepared by dissolving 5 to 10mg of polymer in 10mL (at 160 ℃) of stable TCB (same as mobile phase) and holding for 3 hours with continuous shaking before introduction into the GPC instrument.

I) Degree of crystallinity: the crystallinity was measured on 5 to 10mg, typically 8. + -. 0.5mg samples using a Mettler TA820 Differential Scanning Calorimeter (DSC). The crystallization curve was obtained during a cooling and heating scan at 50 ℃/min between-70 ℃ and 170 ℃.

Examples

The following examples are included to illustrate certain aspects and embodiments of the invention described in the claims. However, those skilled in the art will appreciate that the following description is illustrative only and should not be taken in any way as a limitation of the present invention.

Table 1: materials for use in polymer compositions

Material	Manufacturer/supplier
		Queo 2M1371	Borealis AG
Queo 62002	Borealis AG
		Engage 8842	DOW
VTMS	Evonik resource efficiency GmbH
		CatMB SA	Borealis AG

All commercially available materials refer to these materials available from the manufacturer in 7 months 2018.¹Commercially available as Queo 7001LA in 7 months 2018;²not commercially available.

Table 2: properties of the starting ethylene copolymer

Table 3: unsaturation level of the starting ethylene Polymer

Example 1(Ex1)

A plastomer is prepared by the following process: the polymer (Queo 2M137) was mixed and grafted with various amounts of Vinyltrimethylsiloxane (VTMS) and peroxide and reacted in a co-rotating twin screw extruder at a temperature of 200 ℃ with a residence time of 60 seconds to obtain grafted resins (see table 4).

As the weight percent of VTMS increases, the gel content of the polymer composition also increases.

Compression set specimens were prepared from the tape by compression molding the tape into a template. Tape samples (thickness of 2mm and width of 40 mm) were produced on a Colin extruder (Teach-Line E20T) with a temperature profile of 120-. The material was dry blended (mixed) with 4% CatMB SA and then extruded into a tape.

The uncrosslinked tape was used for template pressing to give a thickness of 6mm for compression set measurement. After the panel was pressed, it was placed in hot water at 50 ℃ for 24h to completely crosslink it. Subsequently, the gel content of the crosslinked plaques was measured using the method described above prior to compression set measurement.

The% compression set results for the plastomer in example 1 are shown in figure 1.

Table 4: gel content of samples containing Queo 2M137 after grafting and crosslinking with varying amounts of VTMS

Examples	Vinyl trimethicone/% w/w	density/Kg/m3	Gel content/% w/w
				1.1	0.5	874.4	71
1.2	1.8	877.3	94
				1.3	2.9	880.1	93

Example 2(Ex2)

Two different base resins, Queo 6200 and Engage 8842, were grafted with approximately the same amount of silane. Engage comprises 3.5 wt% more units derived from 1-octene than Queo 6200. The compression set test was carried out in a similar manner to that described in example 1 (see above).

As can be seen, Queo has a lower comonomer content than Engage. However, the very low, almost negligible crystallinity of Queo makes it very elastic at low temperatures where all chains capable of crystallization will crystallize. At 100 ℃, there is no difference in elasticity between Queo and Engage, since all crystals are molten.

Table 5: compression set performance according to embodiments of the invention