阅读说明：本技术 具有高熔体流动速率的丁烯-1聚合物组合物 (Butene-1 polymer compositions having high melt flow rates ) 是由 R·马尔基尼 S·斯巴塔罗 R·皮卡 于 2018-08-03 设计创作，主要内容包括：一种丁烯-1聚合物组合物,其具有MFR值,为100至300g/10min,根据ISO1133在190℃下以2.16kg的负荷测量,包含：A)丁烯-1均聚物或丁烯-1与一种或多种选自乙烯和高级α-烯烃的共聚单体的共聚物,具有至多5摩尔％的共聚单体含量；B)丁烯-1与一种或多种选自乙烯和高级α-烯烃的共聚单体的共聚物,所述共聚物具有6摩尔％至20摩尔％的共聚单体含量；所述组合物具有相对于A)和B)的总和为4摩尔％至15摩尔％的总共聚单体含量,和以A)和B)的总重量计75重量％或更小的在0℃下可溶于二甲苯的部分的含量。(A butene-1 polymer composition having MFR values from 100 to 300g/10min, measured at 190 ℃ under a load of 2.16kg according to ISO1133, comprising A) a butene-1 homopolymer or a copolymer of butene-1 with one or more comonomers selected from ethylene and higher α -olefins, having a comonomer content of at most 5 mol%, B) a copolymer of butene-1 with one or more comonomers selected from ethylene and higher α -olefins, said copolymer having a comonomer content of from 6 to 20 mol%, said composition having a total comonomer content of from 4 to 15 mol% with respect to the sum of A) and B), and a content of xylene soluble fractions at 0 ℃ of 75% by weight or less, based on the total weight of A) and B).)

1. A butene-1 polymer composition having MFR values from 100 to 300g/10min, preferably from 110 to 300g/10min, more preferably from 150 to 250g/10min, measured according to ISO1133 at 190 ℃ with a load of 2.16kg, and comprising:

A) butene-1 homopolymers or copolymers of butene-1 with one or more comonomers selected from ethylene and higher α -olefins, having a comonomer content (C) of at most 5 mol%, preferably at most 4 mol%_A)；

B) Copolymers of butene-1 with one or more comonomers selected from ethylene and higher α -olefins, having a comonomer content (C) of from 6 to 20 mol%, preferably from 8 to 18 mol%_B)；

The composition has a total comonomer content of 4 to 15 mol%, preferably 5 to 15 mol%, relative to the sum of a) and B), and a content of fraction soluble in xylene at 0 ℃ of 75 wt% or less, preferably 70 wt% or less, based on the total weight of a) and B).

2. Butene-1 polymer composition according to claim 1, from 30% to 70% by weight, preferably from 35% to 65% by weight of a) and from 30% to 70% by weight, preferably from 35% to 75% by weight of B), relative to the total weight of a) and B).

3. The butene-1 polymer composition according to claim 1 having a DH TmII value ranging from 4 to 15J/g, measured with a scanning speed corresponding to 10 ℃/min.

4. Butene-1 polymer composition according to claim 1 having Mw/Mn values, wherein Mw is the weight average molar mass and Mn is the number average molar mass, both measured by GPC, equal to or lower than 3.5.

5. The butene-1 polymer composition according to claim 1 having Mz value of 90,000g/mol or more measured by GPC.

6. The butene-1 polymer composition according to claim 1 having Mw values equal to or greater than 50,000 g/mol.

7. A process for the preparation of the butene-1 polymer composition according to claim 1 comprising at least two successive stages carried out in two or more reactors connected in series, wherein components a) and B) are prepared in separate subsequent stages, operating in each stage except the first stage in the presence of the polymer formed and the catalyst used in the previous stage.

8. The process according to claim 9, carried out in the presence of a metallocene catalyst obtainable by contacting:

-a stereorigid metallocene compound;

-an aluminoxane or a compound capable of forming an alkylmetallocene cation; and optionally (c) a second set of instructions,

-an organoaluminium compound.

9. Article consisting of a butene-1 polymer composition according to claim 1 or 2 or comprising a butene-1 polymer composition according to claim 1 or 2.

10. The article of claim 9 in the form of a film or fiber.

11. A hot melt adhesive composition consisting of the butene-1 polymer composition according to claim 1 or 2 or comprising the butene-1 polymer composition according to claim 1 or 2.

Technical Field

The present disclosure relates to a butene-1 polymer composition having a melt flow rate not less than 100g/min, measured according to standard ISO1133 at 190 ℃ with a load of 2.16kg, thus having high flowability in the molten state.

Butene-1 polymer compositions provide high tensile properties, low hardness, low flexural modulus and low glass transition temperature while still maintaining measurable crystallinity.

The butene-1 polymer compositions of the present invention have many applications. In particular, the butene-1 polymer compositions of the invention can be used for the production of films and fibers, as a component of hot-melt adhesives, as a polymer additive to enhance the rheological, mechanical and optical properties of polymer compositions, or as a fluidizing agent for lubricants.

Background

Butene-1 polymers with high melt flow rates are disclosed in the art, in particular in US4677025, US4960820, WO2006045687, WO2015074830 and EP 0314495. Due to their valuable properties (e.g. chemical inertness, mechanical properties and nontoxicity), these polymers have been used in many fields of application.

In particular, butene-1 polymers having high melt flow rates are useful for the production of films and fibers, optionally blended with other polyolefins, and in various hot melt formulations due to their high flowability in the molten state and their physical properties.

As described in US4677025, the molecular weight and molecular weight distribution of butene-1 polymers have an effect on the final polymer properties.

It has now been found that by combining at least two butene-1 polymers having different and specific comonomer contents, and by suitably selecting the melt flow rate and optionally the molecular weight and molecular weight distribution, this can be achieved by using metallocene catalysts, an advantageous property profile is obtained.

Disclosure of Invention

Accordingly, the present disclosure provides a butene-1 polymer composition having a melt flow rate value of from 100 to 300g/10min, preferably from 110 to 300g/10min, more preferably from 150 to 250g/10min, measured according to ISO1133 at 190 ℃ with a load of 2.16kg (hereinafter "MFR") and comprising:

A) butene-1 homopolymers or copolymers of butene-1 with one or more comonomers selected from ethylene and higher α -olefins, having a comonomer content (C) of at most 5 mol%, preferably at most 4 mol%_A)；

B) Copolymers of butene-1 with one or more comonomers selected from ethylene and higher α -olefins, having a comonomer content (C) of from 6 to 20 mol%, preferably from 8 to 18 mol%_B)；

The composition has a total comonomer content of 4 to 15 mol%, preferably 5 to 15 mol%, relative to the sum of a) and B), and a content of fraction soluble in xylene at 0 ℃ of 75 wt% or less, preferably 70 wt% or less, based on the total weight of a) and B).

The butene-1 polymer compositions provided herein can be obtained directly in the polymerization without the need to use free radical generators such as peroxides to increase the MFR value, thus avoiding chemical contamination and unpleasant odor caused by the introduction of free radical generators.

Such butene-1 polymer compositions have low hardness, low flexural modulus, high elongation at break values and low glass transition temperatures, which are useful properties in films and fibers, wherein the butene-1 polymer compositions of the present invention are useful for blending with other polyolefins, in particular propylene polymers, commonly used for the production of said articles, and also in hot melt compositions.

Detailed Description

For the butene-1 polymer compositions provided herein, the specific amount of xylene soluble fraction at 0 ℃ (expressed as the weight content of the fraction measured by extraction, based on the total weight of a) and B)) is from 35 to 75 wt. -%, or from 35 to 70 wt. -%, in particular from 40 to 70 wt. -%, or from 40 to 65 wt. -%.

When A) is a copolymer, the specific lower limit of the comonomer content is 1 mol%.

Preferably, when both a) and B) are copolymers, the difference between the percentage values of the comonomer content of B) and a) satisfies the following relationship:

C_B)-C_A) Not less than 5; or

C_B)-C_A)≥6。

The relative amounts of components A) and B) can be readily determined depending on the desired value of the total comonomer content, the comonomer content of the individual components and the content of their xylene-soluble fraction at 0 ℃.

Preferred amounts are from 30 to 70% by weight, preferably from 35 to 65% by weight, of A) and from 30 to 70% by weight, preferably from 35 to 75% by weight, of B), all relative to the total weight of A) and B).

In addition to or as an alternative to ethylene, a specific example of a higher α -olefin which may be present as a comonomer in components A) and B) is of the formula CH₂α -alkenes of CHR, where R is methyl or alkyl containing 3-8 or 3-6 carbon atoms, e.g. propene, hexene-1, octene-1.

However, ethylene is a preferred comonomer, especially for component B).

The butene-1 polymer compositions of the present invention have a measurable crystallinity as evidenced by the presence of a melting temperature peak of the crystalline butene-1 polymer in a Differential Scanning Calorimetry (DSC) pattern.

In particular, the butene-1 polymers of the present invention show one or more melting peaks in the second DSC heating scan. These temperature peaks generally occur at a temperature equal to or lower than 90 ℃, or equal to or lower than 85 ℃, in particular from 40 ℃ to 90 ℃, or from 45 ℃ to 85 ℃, due to the melting point of form II of the butene-1 polymer (TmII), and the area under the peak(s) is taken as the total enthalpy of fusion (DH TmII). However, if there is more than one peak, the highest (strongest) peak is taken as TmII.

The butene-1 polymers according to the invention have specific overall DH TmII values of 15J/g or less, in particular from 4 to 15J/g, measured at a scanning speed corresponding to 10 ℃/min.

Furthermore, the butene-1 polymers of the invention show one or more melting peaks, generally occurring in the DSC heating scan carried out after ageing at temperatures equal to or lower than 100 ℃, or equal to or lower than 98 ℃, in particular from 30 ℃ to 100 ℃, or from 30 ℃ to 98 ℃. Such temperature peak or peaks are attributed to the melting point of form I of butene-1 polymer (TmI) and the area under the peak(s) as the total enthalpy of fusion (DH TmI). However, if there is more than one peak, the highest (strongest) peak is taken as TmI.

The butene-1 polymers according to the invention have specific overall DH TmI values of 50J/g or less, in particular from 25 to 50J/g, or from 30 to 50J/g, measured at a scanning speed corresponding to 10 ℃/min.

The butene-1 polymers of the present invention may also have detectable levels of crystalline form III. Form III can be detected by X-ray diffraction methods, which are described in journal of polymer science B: the polymers were described in Journal of Volume 1, phase 11, page 587-591, 11 months of 1963 (Journal of Polymer Science Part B: Polymer Letters Volume 1, Issue 11, pages587-591, November 1963), or Macromolecules, Volume 35, No.7, 2002 (Macromolecules, Vol.35, No.7, 2002).

The butene-1 polymers according to the invention have specific X-ray crystallinity values ranging from 10% to 50%, in particular from 15% to 45%.

The specific MFR values of components a) and B) may be widely selected, provided that said MFR values of the entire composition are obtained.

In this respect, it is well known that the logarithm of the MFR value of a polyolefin blend (and therefore also of a butene-1 polymer) is generally given by the sum of the products of the weight fractions of the individual components and the logarithm of the MFR value.

Thus, the MFR value of a composition made from the blend of components a) and B) is determined by the following relationship:

log MFR(A+B)＝wA log MFR(A)+wB log MFR(B)

wherein MFR (A + B) is the MFR value of the blend of A) and B), MFR (A) and MFR (B) are the MFR values of components A) and B), respectively, and wA and wB are the respective weight fractions. For example, when the blend is made of 50 wt% of component a) and 50 wt% of component B), wA and wB are both 0.5.

However, in order to obtain good flowability in the molten state, it is preferred to keep the MFR values of the individual components A) and B) sufficiently high, in particular in the range from 50 to 400g/10min, or from 80 to 350g/10 min.

Furthermore, the butene-1 polymer composition of the present invention preferably has at least one of the following further characteristics:

-an Intrinsic Viscosity (IV), measured in Tetrahydronaphthalene (THN) at 135 ℃, equal to less than 0.70dl/g, or equal to or less than 0.65dl/g, in particular from 0.50dl/g to 0.70dl/g or from 0.50dl/g to 0.65 dl/g;

-Mw/Mn values, where Mw is the weight average molar mass and Mn is the number average molar mass, both measured by GPC (gel permeation chromatography), equal to or lower than 3.5, or equal to or lower than 2.5, with a lower limit in each case of 1.5;

-a Mz value of 90,000g/mol or more, or 100,000g/mol or more, in particular from 90,000 to 200,000g/mol or from 100,000 to 190,000 g/mol;

-Mw, equal to or greater than 50,000g/mol, or equal to or greater than 70,000g/mol, in particular from 50,000 to 180,000g/mol, or from 70,000 to 150,000 g/mol;

operating at 150.91MHz¹³Isotactic pentads (mmmm) measured by C-NMR, higher than 90%; in particular higher than 93% or higher than 95%;

-4, 1 inserts undetectable with 13C-NMR operating at 150.91 MHz;

-yellowness index, lower than 0; in particular from 0 to-10 or-1 to-9 or-1 to-5;

-a shore D value, equal to or lower than 50, or equal to or lower than 45, in particular from 15 to 50 or from 15 to 45;

-a tensile stress at break, measured according to ISO527, ranging from 10MPa to 45MPa, in particular from 10MPa to 35 MPa;

-a tensile elongation at break, measured according to ISO527, of from 400% to 900%; in particular from 450% to 700%;

a glass transition temperature of-19 ℃ or less, in particular-20 ℃ or less, with a lower limit of-23 ℃.

A density of 0.880g/cm³Or greater, particularly 0.885g/cm³Or greater; wherein the upper limit is 0.910g/cm³Or 0.899g/cm³；

The butene-1 polymer components a) and B) are obtainable by polymerizing monomers in the presence of a metallocene catalyst system obtainable by contacting:

-a stereorigid metallocene compound;

-an aluminoxane or a compound capable of forming an alkylmetallocene cation; and optionally (c) a second set of instructions,

-an organoaluminium compound.

Preferably, the stereorigid metallocene compound belongs to the following formula (I):

wherein:

m is an atom selected from transition metals belonging to group 4; preferably M is zirconium;

x, equal to OR different from each other, are a hydrogen atom, a halogen atom, R, OR' O, OSO₂CF₃、OCOR、SR、NR₂Or PR₂Group, wherein R is linear or branched, saturated or unsaturated C₁-C₂₀Alkyl radical, C₃-C₂₀Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Alkylaryl or C₇-C₂₀Arylalkyl, optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements; and R' is C₁-C₂₀Alkylene radical, C₆-C₂₀Arylene radical, C₇-C₂₀Alkylarylene or C₇-C₂₀An arylalkylene group; preferably, X is a hydrogen atom, a halogen atom, OR' O OR R group;more preferably X is chloro or methyl;

R¹、R²、R⁵、R⁶、R⁷、R⁸and R⁹Identical or different from each other, is a hydrogen atom, or a linear or branched, saturated or unsaturated C₁-C₂₀Alkyl radical, C₃-C₂₀Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Alkylaryl or C₇-C₂₀Arylalkyl, optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements; or R⁵And R⁶And/or R⁸And R⁹May optionally form a saturated or unsaturated 5-or 6-membered ring, which may carry C₁-C₂₀Alkyl as a substituent; provided that R is⁶Or R⁷Is straight or branched, saturated or unsaturated C₁-C₂₀Alkyl, optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements; preferably C₁-C₁₀An alkyl group;

R³and R⁴Equal to or different from each other, is a linear or branched, saturated or unsaturated C₁-C₂₀Alkyl, optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements; preferably R³And R⁴Are identical or different from each other as C₁-C₁₀An alkyl group; more preferably R³Is methyl or ethyl; r⁴Is methyl, ethyl or isopropyl.

Preferably, the compound of formula (I) has formula (Ia):

wherein:

M、X、R¹、R²、R⁵、R⁶、R⁸and R⁹As described above;

R³is straight-chain or branched, saturated or unsaturated C₁-C₂₀Alkyl, optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements; preferably R³Is C₁-C₁₀An alkyl group; more preferably R³Is methyl or ethyl.

Specific examples of metallocene compounds are dimethylsilyl { (2, 4, 7-trimethyl-1-indenyl) -7- (2, 5-dimethyl-cyclopenta [1, 2-b: 4, 3-b' ] -dithiophene) } zirconium dichloride; dimethylsilanediyl { (1- (2, 4, 7-trimethylindenyl) -7- (2, 5-dimethyl-cyclopenta [1, 2-b: 4, 3-b '] -dithiophene) } zirconium dichloride and dimethylsilanediyl { (1- (2, 4, 7-trimethylindenyl) -7- (2, 5-dimethyl-cyclopenta [1, 2-b: 4, 3-b' ] -dithiophene) } zirconium dimethyl.

Examples of alumoxanes are Methylalumoxane (MAO), tetra- (isobutyl) alumoxane (TIBAO), tetra- (2, 4, 4-trimethylpentyl) alumoxane (TIOAO), tetra- (2, 3-dimethylbutyl) alumoxane (TDMBAO) and tetra- (2, 3, 3-trimethylbutyl) alumoxane (TTMBAO).

Examples of compounds capable of forming an alkylmetallocene cation are compounds of the formula D + E-, wherein D is⁺Is a bronsted acid, capable of donating a proton and reacting irreversibly with a substituent X of the metallocene of formula (I), and E-is a compatible anion, which is capable of stabilizing the active catalytic species originating from the reaction of the two compounds, and which is sufficiently labile to be removed by the olefin monomer. Preferably, the anion E-contains one or more boron atoms.

Examples of organoaluminum compounds are Trimethylaluminum (TMA), Triisobutylaluminum (TIBA), tris (2, 4, 4-trimethylpentyl) aluminum (TIOA), tris (2, 3-dimethylbutyl) aluminum (TDMBA) and tris (2, 3, 3-trimethylbutyl) aluminum (TTMBA).

Examples of such catalyst systems and polymerization processes using such catalyst systems can be found in WO2004099269 and WO 2009000637.

By operating under known polymerization conditions in the presence of the above-mentioned catalysts, the two components A) and B) of the butene-1 polymer composition of the invention can be prepared separately and then blended together in the molten state by using known polymer processing devices such as single-screw and twin-screw extruders.

However, as previously mentioned, the butene-1 polymer compositions of the present invention may be prepared directly in the polymerization.

Thus, the polymerization process for preparing the composition comprises at least two successive stages carried out in two or more reactors connected in series, in which components a) and B) are prepared in separate subsequent stages, operating in each stage except the first stage in the presence of the polymer formed and the catalyst used in the preceding stage.

The polymerization process may be carried out in the liquid phase, optionally in the presence of an inert hydrocarbon solvent, or in the gas phase, using a fluidized bed or a mechanically stirred gas phase reactor.

The catalyst may be added to the first reactor only, or to more than one reactor.

The hydrocarbon solvent may be aromatic (e.g., toluene) or aliphatic (e.g., propane, hexane, heptane, isobutane, cyclohexane, 2, 4-trimethylpentane, and isododecane).

Preferably, the polymerization process is carried out by using liquid butene-1 as polymerization medium. The polymerization temperature may be from 20 ℃ to 150 ℃, in particular from 50 ℃ to 90 ℃, for example from 65 ℃ to 82 ℃.

Concentration of hydrogen (molar ppm H) in the liquid phase during polymerization₂Butene-1 monomers) are generally from 1000ppm to 1900ppm, in particular from 1100ppm to 1800 ppm.

When preparing the copolymer, the amount of comonomer, in particular ethylene, in the liquid phase may be from 0.1 to 8 wt%, in particular from 0.2 to 6 wt%, relative to the total weight of comonomer and butene-1 monomer present in the polymerization reactor.

In particular, the amount of comonomer may be from 0.1 to 0.9 or from 0.2 to 0.8% by weight for the preparation of component a) and from 1 to 8 or from 1.5 to 6% by weight for the preparation of component B).

In hot melt adhesive applications, the butene-1 polymer compositions of the present invention may optionally be blended with other materials commonly used in the relevant art.

In particular, in addition to the butene-1 polymer composition of the invention comprising components a) and B), the hot melt adhesive polyolefin composition may comprise one or more of the following optional components:

I) at least one additional polymer, in particular selected from amorphous poly- α -olefins, thermoplastic polyurethanes, ethylene/(meth) acrylate copolymers, ethylene/vinyl acetate copolymers and mixtures thereof;

II) at least one resinous material different from (I) and selected from the group consisting of aliphatic hydrocarbon resins, terpene/phenolic resins, polyterpenes, rosins, rosin esters and derivatives thereof, and mixtures thereof;

III) at least one wax or oil, in particular chosen from mineral, paraffinic or naphthenic waxes or oils; and

IV) a nucleating agent.

Examples of nucleating agents are isotactic polypropylene, polyethylene, amides such as stearamide or talc.

When present and independent of each other, the preferred weight amounts of the optional components, relative to the total weight of the hot melt adhesive polyolefin composition, are:

-from 0.1 to 25% by weight, in particular from 1 to 25% by weight, of I);

-10 to 75 wt.%, in particular 10 to 40 wt.% of II);

0.1 to 50% by weight, in particular 1 to 30% by weight, of III);

-IV from 0.01 to 1% by weight, in particular from 0.1 to 1% by weight).

The components can be added and blended in the molten state with the butene-1 polymer composition of the present invention by using known polymer processing devices such as single and twin screw extruders.

The hot melt adhesive composition can be used in several fields, such as the paper and packaging industry, furniture manufacture, e.g. for edge banding, especially square edges, and soft forming applications, for paneling in high humidity environments and for the production of nonwoven articles such as disposable diapers.