CN100460475C

CN100460475C - Novel multifunctional polymer for use in hot melt adhesive applications

Info

Publication number: CN100460475C
Application number: CNB2004800200110A
Authority: CN
Inventors: A·哈桑; G·博辛格; T·P·卡里亚拉
Original assignee: HRD Corp
Current assignee: HRD Corp
Priority date: 2003-05-19
Filing date: 2004-05-19
Publication date: 2009-02-11
Anticipated expiration: 2024-05-19
Also published as: CN1823149A

Abstract

Adhesives comprising one or more tackifiers, ethylene vinyl acetate copolymers ('EVA') and a low viscosity, low number average molecular weight (M<SUB>n </SUB>between 700 and less than 1000) ethylene/alpha-olefin interpolymer which has wax-like properties, and produced using a single metallocene catalyst system, were formulated, and have adhesive characteristics over a broad temperature range. These hot melt adhesive compositions ('HMAs') have properties comparable to those of commercially available, three component HMAs comprising ethylene vinyl acetate polymers, tackifier and wax. HMA embodiments include those wherein the ethylene/alpha-olefin interpolymers comprise ethylene and propylene as copolymers, and the interpolymer has a low Brookfield viscosity, between 20-50 centipoise at 300 DEG F.

Description

The novel multifunctional polymer that is used for use in hot melt adhesive applications

The cross reference of related application

The application requires the right of U.S. Provisional Patent Application series number 60/471,318 that proposed on May 19th, 2003 and the non-temporary patent application series number 10/666,488 of the U.S. that proposed on September 19th, 2003, and their content is incorporated this paper into as a reference at this.

Technical field

The present invention is a kind of new-type heat-melting binder composition that mainly is made of selected ethylene/alpha-olefin interpolymer (interpolymer) and one or more optional tackifier.With by three kinds of independent components---what traditional hot fusibleness tackiness agent that polymkeric substance, wax and tackifier constitute was different is that hot-melt adhesive of the present invention has used ethylene/alpha-olefin interpolymer.Carefully select the composition and the character of described interpolymer, thereby make it in binder composition, play the effect of polymkeric substance and wax simultaneously.Therefore, use described tackiness agent for low viscosity and can contain single component, perhaps the described tackiness agent of application for needs interpolation tackifier can contain simple two kinds of components.

Background technology

Hotmelt (" HMA ' S ") be prevalent in many commercial fields, being included between substrate and the another kind of article needs agglutinating user and industrial packaging.They usually are used to make Corrugated Box, box etc.They also are used for following multiple field, for example bookbinding; Paper bag seals; Furniture is made; The manufacturing of shaving board, liner board, various other paper product; And be used for bonding other goods, for example glass, metal and various plastics comprise paper label is attached on the plastic containers.Other purposes of hot-melt adhesive also comprises carpet seam envelope band, laminate, group of products component, non-woven constructions and perfusion and encapsulation (potting and encapsulation) compound.

Because these different purposes just require hot-melt adhesive to keep high adherence in very big temperature condition scope.For example, in manufacturing shipping refrigeration or frozen product or the Corrugated Box that the food of packing is used in ice, can select hotmelt widely, because they can keep high adherence under cold condition.Yet in other purposes, hot-melt adhesive may keep the strong binding property with substrate under extreme weight and operation vibrations and high humidity.

Different with other tackiness agent that the solution form of common conduct in certain solvent used, HMA ' s is solid normally, and in commercial use, is coated on the substrate with molten state under about 350 ℉ usually.Along with the fused adhesive cools and when solidifying, between substrate and another kind of object, just form bonding.Can use various technology that hotmelt is coated on the substrate, comprise coating roller, knife coater and atomizer.

Other two important factors are so-called tackiness agent " set time " (set time) and " open hour " (open time) in the hot melt adhesive performance." open hour " of hot-melt adhesive are that tackiness agent is cured to the time that is spent when no longer boning with slated items." set time " of hot-melt adhesive be adhesive cools to have sufficient intensity to form required time when bonding.Curing speed is an important parameters for the application of high-speed packet wiring and so on, and these application needs are bonding rapidly to avoid producing the very poor or unencapsulated box of sealing.

Most hot-melt adhesives are ternary mixtures: wax, tackifier and polymer resin.Although every kind of component exists ratio about equally, also their relative ratios is carried out " fine setting " usually according to the needs of application-specific in the HMA prescription.

Polymeric constituent provides intensity for bonding.Tackifier come for tackiness agent provides viscosity by improve wettability (it is used to guarantee make article to bond) when tackiness agent solidifies, and reduce the viscosity of this system, make that tackiness agent is easier to be coated on the substrate.Wax has shortened the open hour and has reduced the viscosity of this system.Generally speaking, make the per-cent of the wax of existence minimize the amount that makes its interpolation simultaneously and be enough to realize required viscosity and curing speed.

Many hot melt adhesive formulations things adopt vinyl-acetic ester (" VA ") polymkeric substance to make polymeric constituent, and prescription is according to the difference of vinyl acetate content in the polymkeric substance and difference.Because lower cost, the polymkeric substance of low acetate vinyl acetate content is preferred, and because they are nonpolar relatively, they can relative nonpolar tackifier with other and the wax preparation to produce compatible prescription.When in the hot melt adhesive formulations thing, using the fluoropolymer resin (vinyl acetate content is greater than about 18%) of higher vinyl acetate content, can produce stronger ionic bond, make stronger tackiness agent thus with the polarity substrate of paper and so on.Yet, use the polymkeric substance of higher vinyl acetate content to require to prepare to keep the consistency of formulation with polarity higher wax and tackiness agent.The wax that polarity is higher, for example Fischer-Tropsch wax is more expensive than paraffin usually, and the selection of the higher wax of these polarity and supply limited.The supply failure that they are difficult to domestic acquisition and therefore may suffer to cause because of world's current events.

Except adherent needs, HAM ' s also needs performance such as the heat and the oxidative stability in other field.Hotmelt applies with molten state, and therefore many application all comprise long-time exposure at high temperature.Good heat and oxidative stability are meant that HMA can blackening can not produce yet and burn or epidermis or gel that it can not show bigger viscosity in time yet and change.This charing, skinning, gel formation and/or viscosity change the tendency that also can improve prescription blocking pipe and nozzle when industrial application for example.In the HMA formulation, add the higher wax of any wax, especially polarity, can reduce the heat and the oxidative stability of formulation.

The hot-melt adhesive that is made of the ethene polymers that does not contain vinyl-acetic ester is disclosed in the prior art.For example, the United States Patent (USP) 5 of authorizing people such as Foster of on June 4th, 1991 issue, 021, disclose a kind of viscosity under 135 ℃ for No. 257 and be approximately 3000 to about 25000 centipoises, and ring and ball softening point is approximately 90 ℃ to about 125 ℃ hot-melt adhesive composition, described binder composition contains by at least a essentially amorphous propylene/hexene copolymer, the blend that at least a tackifier are formed, and also comprises at least a basic crystallization, low viscous chloroflo.

The United States Patent (USP) 5 of authorizing people such as Tse of on June 25th, 1996 issue; 530; No. 054 claimed a kind of hot-melt adhesive composition, described composition is made of following material substantially: (a) ethene of 30wt% to 70wt% and the approximately C of the extremely about 30wt% of 6wt% ₃-C ₂₀The multipolymer that alpha-olefin makes in the presence of the catalyst composition that contains metallocenes and alumina sol (aikyiaiurnirsoxan beta), described multipolymer have about 20,000 to about 100,000 Mw; (b) be selected from the hydrocarbon tackifier of enumerating list.

The U.S. Patent number 5 of authorizing people such as Tse of on August 20th, 1996 issue; 548; 014 asks for protection a kind of hot-melt adhesive composition; it contains the blend of ethylene/alpha-olefin copolymer, and wherein the Mw of first multipolymer from about 20,000 to about 39; 000; the Mw of second multipolymer from about 40,000 to about 100,000.The every kind of hot-melt adhesive that exemplifies all contains copolymer blend, and wherein the polymolecularity of at least a multipolymer is greater than 2.5.In addition, the concrete proportion of the multipolymer of the least density that is exemplified is 0.894g/cm ³

United States Patent (USP) 6,107, the 430 disclosed hot-melt adhesives of authorizing people such as Dubois of on August 22nd, 1991 issue contain ethene and at least a C ₂-C ₂₀(its density is 0.850 to 0.895g/cm at least a even line style of alpha-olefin interpolymer or substantial linear interpolymer ³), optional at least a tackifying resin; With optional at least a wax, wherein the viscosity of hot-melt adhesive under 150 ℃ is lower than about 5000 centipoises.

Same, the disclosed hot-melt adhesive of EP 0 886656 B1 of authorizing people such as Simmons of September 19 calendar year 2001 issue contains 5 to 95wt% ethene and at least a alpha-olefin interpolymer, and (it has 1.5 to 2.5 polydispersity index, Mw/Mn and 0.850 is to 0.885g/cm ³Density) at least a even line style or substantial linear interpolymer, 5 to 95wt% at least a tackifying resin; With optional at least a wax.

Tse is at Application of Adhesion Model for Developing Hot MeltAdhesives Bonded to Polyolefin Surfaces, Journal of Adhesion, Vol.48, Issue1-4, pp.149-167, point out in 1995, compare with hot-melt adhesive based on vinyl-vinyl acetate copolymer, hot-melt adhesive based on even line style ethylene/alpha-olefin interpolymer shows higher viscosity and relatively poor tensile strength, but have higher bond strength with polyolefin surfaces, higher breaking stress and lower yielding stress are arranged.

Can make the hot-melt adhesive that contains these polymkeric substance, it is suitable with the strength property of HMA formulation that contains vinyl-acetic ester, but they make gained thermally melting formulation more thermally-stabilised than the hot-melt adhesive that contains vinyl-acetic ester with the ability of nonpolar tackifier preparation.

Yet, the prior art that relates to the prior art of vinyl-acetic ester based adhesive and relate to the polymer-based carbon tackiness agent of non-vinyl-acetic ester does not all expect the present invention, has made by the present invention a kind ofly can replace the wax of hot melt adhesive agent prescription and the synthetic polymer of polymeric constituent simultaneously separately.

Thisly constitute and can be extremely beneficial with the low-cost hot melt adhesive agent prescription of molten form shipping and unloading by single component (beyond the tackifier).It also is extremely beneficial can also making the cost of formulation and the minimum HMA prescription of volatility thus with minimum mixing step preparation.It also is extremely beneficial having following HMA formulation: it can be suitable with the bond properties of the HMA that comprises the high VA that contains ethane-acetic acid ethyenyl ester (" EVA "), but do not need to add main body entrance and/or the petroleum wax of the costliness made by import oil base raw material.If this hot-melt adhesive formulation can show the intensity and the adhesion characteristic of the formulation that contains EVA, also have good heat and oxidative stability simultaneously, that also is extremely beneficial.

HMA of the present invention contains single polymeric constituent, the effect that it had not only played the effect of polymkeric substance but also played wax, and can be easily with molten state shipping and/or unloading.Use for low viscosity,, and, can add one or more tackifier for the application of higher tack without any need for other component.Thus, HMA composition of the present invention needs minimum mixing step, and each step all can increase the additional cost and the volatility of final HMA formulation.HMA composition of the present invention need not use expensive polar waxes can play a role in formulation yet.

HMA composition of the present invention also shows the bonding and strength property suitable with the hot-melt adhesive of the commercially available EVA of containing, also shows good heat and oxidative stability.In addition, HMA composition of the present invention provides a kind of composition, when described this composition is used for subsequently the regenerated consumer packaging, owing to eliminated the wax component and/or reduced tackify dosage, is easier to regeneration than traditional hot fusibleness tackiness agent.

At last, formulation of the present invention provides a kind of and has been used for hot-melt adhesive and is used for the composition of paper coating, and it has usually by Food and Drug Administration (Food and DrugAdministration) thinks safe character.

Summary of the invention

The present invention includes the hot-melt adhesive composition that contains one or more tackifier and ethylene/alpha-olefin interpolymer.Use the synthetic rapid compound of these ethylene/alpha-olefins of list or bimetal cyclopentadienyl catalyst polymerization.

One embodiment of the invention are the hot-melt adhesive compositions that mainly are made of following material:

A) the even ethylene/alpha-olefin interpolymer of (in the hot-melt adhesive composition final weight) about 40 to 100wt%; With

B) one or more tackifier of (in the hot-melt adhesive composition final weight) 0 to about 60wt%.

In another embodiment, the present invention is a kind of hot-melt adhesive composition, wherein

A) evenly the amount of ethylene/alpha-olefin interpolymer is (in the hot-melt adhesive composition final weight) about 60 to about 85wt%, and this even ethylene/alpha-olefin interpolymer is characterised in that to have;

I) about 0.880 to about 0.930g/cm ³Density;

Ii) about 1,000 to about 9,000 number-average molecular weight (Mn); With

Iii) about 500 brookfield viscosity (under 300 ℉, measuring) to about 7,000 centipoises and

B) amount of one or more tackifier is (in the hot-melt adhesive composition final weight) about 15 to about 40wt%; And wherein

C) hot-melt adhesive composition is characterised in that and has;

I) about 400 brookfield viscosity (under 350 ℉, measuring) to about 2,000 centipoises;

Ii) more than or equal to the release adhesive fail temperature (Peel AdhesionFailure Temperature " PAFT ") of 110 ℉; With

Iii) more than or equal to the shear adhesion fail temperature (Shear AdhesionFailure Temperature " SAFT ") of 140 ℉.

In the third embodiment, the present invention is a kind of hot-melt adhesive composition, wherein

A) evenly ethylene/alpha-olefin interpolymer is characterised in that to have:

I) about 0.893 to about 0.930g/cm ³Density;

Ii) about 1,000 to about 6,000 number-average molecular weight (Mn); With

Iii) about 1,500 brookfield viscosity (under 300 ℉, measuring) to about 5,000 centipoises; And

B) hot-melt adhesive composition is characterised in that:

I) have about 400 brookfield viscosity (under 350 ℉, measuring) to about 1,400 centipoise;

Ii) has release adhesive fail temperature (" PAFT ") more than or equal to 90 ℉; With

Iii) has shear adhesion fail temperature (" SAFT ") more than or equal to 200 ℉; With

Iv) show 100% paper tear (paper tear) at 120 ℉.

Test the adhesion characteristic of hot-melt adhesive composition of the present invention (" HMA "), it is suitable with the commercially available three component hot-melt adhesive formulation that comprise polymkeric substance, wax and tackifier.

Detailed Description Of The Invention

Unless indicate separately, adopt following test procedure and definition:

Melting index (I ₂), measure 190 ℃/2.16 kilograms of conditions (being called " condition (E) " on formal) according to ASTM D-1238.

Use gel permeation chromatography (GPC) to go up determining molecular weight at the Waters150 ℃ of high temperature chromatogram arrangements (under 140 ℃ system temperature, operating) of being furnished with three mixing porous posts (PolymerLaboratories103,104,105 and 106).Solvent is 1,2, and the 4-trichlorobenzene is used for injection by its 0.3wt% solution for preparing sample.Flow velocity is 1.0 ml/min, and injection volume is 100 microlitres.

Use the elution volume deduced molecular weight measured value of narrow molecular weight distributions polystyrene standards (from Polymer Laboratories) in conjunction with them.Use determines that to polyethylene and the suitable mark-Hao Brunswick coefficient of polystyrene molecular weight of polyethylene of equal value is (as Williams and Word at Journal of Polymer Science, Polymer Letters, Vol.6 is described in (621) 1968) to draw following formula:

M _Polyethylene=a* (M _Polystyrene) b.

In this formula, a=0.4316, b=1.0.Calculate weight-average molecular weight M according to following formula in due form _W: M _W=∑ W _i* M _i, W wherein _iAnd M _iBe respectively the weight fraction and the molecular weight of the i kind cut of wash-out from the GPC post.

Melt viscosity uses the Brookfield VII+ of D. Lab viscometer to measure in disposable aluminium sample chamber according to follow procedure.Used axle (spindle) is the SC-31 thermally melting axle that is fit to the viscosity in 10 to 100, the 000 centipoise scopes of measuring.Use cutting blade that sample is cut into enough little small pieces with in the 1 inch wide 5 inches long sample chambers of packing into.Sample is placed the chamber, this chamber is inserted in the Brookfield well heater and with looper head pliers (needle-nose pliers) fix again.There is the groove of applying Brookfield heater base the sample chamber in the bottom, to guarantee that can not overturn in this chamber when axle is inserted and rotate.Sample is heated to temperature required, for example 300 ℉ or 350 ℉ append sample until fusing sample approximately to below, top, sample chamber 1 inch again.Viscometer apparatus is reduced and axle is immersed in the sample chamber.Continue to descend and on well heater, aim at (align) until the carriage on the viscometer.Viscometer is opened, and be set as and make the shearing rate of torque reading between 30 to 60%.Per minute is got single reading, carried out about 15 minutes, and perhaps until its value stabilization, the record last reading.

Use TA-Q1000 by determine with dsc method degree of crystallinity.Can calculate degree of crystallinity with following formula:

C％＝(A/292J/g)×100，

Wherein per-cent C represents degree of crystallinity, and A represents the melting heat of ethene, and unit is joule/gram (J/g).

According to ASTM D-792 measuring density.Before measuring, sample was calcined 24 hours under envrionment conditions.

Use nucleus magnetic resonance (NMR) spectral method to measure comonomer and monomeric mixing.The use follow procedure is used ¹³C NMR assay determination ethylene content and co-monomer content: ¹³C NMR analyzes

In 10 millimeters NMR pipes, about 3 50/50 mixtures (promptly being the 0.025M in Acetyl Acetone acid chromium (relaxation agent)) that restrain tetrachloroethane-d2/ orthodichlorobenzenes are joined in the 0.4 gram polymer samples, prepare sample thus.By managing and inclusion is heated to 150 ℃ and makes sample dissolution and homogenizing.Use HIGH RESOLUTION SUPERCONDUCTING nuclear magnetic resonance spectrometer (Varian UnityPlus) 400MHz spectrometer (to be equivalent to 100.4MHz's ¹³The C resonant frequency) collects data.Select detecting parameter with guarantee exist under the situation of relaxation agent quantitatively ¹³The C data gathering.Use gate ¹H uncouples, every data file 4000 transient states, 6 pulse per second (PPS) duplicate delays, 24, and the file size of 200Hz spectrum width and 32K data point is heated to 130 ℃ with probe, obtains data thus.

Term " interpolymer " is used in reference to multipolymer or terpolymer etc. herein.That is to say, make a kind of other comonomer and ethylene copolymer at least to make described interpolymer.

Term " narrow composition distribution " is used to describe the comonomer distribution of uniform copolymers herein.Narrow composition is evenly distributed interpolymer also can be by its SCBDI (short-chain branch dispersion index) or CDBI (forming the distribution branch index) sign.SCBDI or CBDI are meant 50% the weight percent with interior polymer molecule of co-monomer content in the total mole of intermediate value co-monomer content.

Can calculate the CDBI of polymkeric substance at an easy rate by the data that obtain by technology known in the art, these technology for example, as Wild etc., Journal Of Polymer Science, Poly.Phys.Ed., Vol.20, p.441 (1982) or United States Patent (USP) 5, intensification elution fractionation method (being abbreviated as " TREF " herein) described in 548,014, their disclosed contents are incorporated herein by this reference.Therefore, can use the follow procedure that calculates CDBI:

(1) produces the copolymer concentration that obtains by TREF stdn cumulative distribution table to eluting temperature.

(2) eluting temperature during the 50wt% dissolving multipolymer of having measured wash-out.

(3) be determined at the molar content of comonomer in the multipolymer cut of this centre eluting temperature wash-out.

(4) 0.5 times and 1.5 times restriction molar part numerical value of calculating comonomer molar content in the multipolymer cut of this medium temperature wash-out.

(5) measure and the relevant restriction eluting temperature value of these restriction molar part numerical value.

(6) the accumulation eluting temperature distribution part of skew integration between these restriction eluting temperature values.

(7) with the result of skew integration, CDBI is as the per-cent of primary stdn cumulative distribution table.

A) even ethylene/alpha-olefin interpolymer component

Use term " uniform copolymers " to be meant herein and use line style or the substantial linear ethenyl copolymer that limits geometrical shape or the preparation of single-point metalloscene catalyst.Term evenly be meant any comonomer all in given interpolymer molecule in stochastic distribution and this interpolymer nearly all interpolymer molecule all have identical ethene/comonomer ratio.Measure by dsc (DSC), evenly the melting peak of line style and substantially linear ethylene polymers can reduce and/or along with number-average molecular weight reduces and broadens along with density.

Evenly line style or substantially linear ethylene polymers are characterised in that to have narrow molecular weight distributions (Mw/Mn).For line style and substantial linear ethylene copolymer, Mw/Mn is preferably 1.5 to 2.5, and preferred 1.8 to 2.2.Yet some interpolymer of the present invention can have much bigger Mw/Mn value and still show excellent binding property.

Be important to note that the available ethene polymers is different with the new LDPE (film grade) of high-pressure process preparation among the present invention.On the one hand, new LDPE (film grade) is that density is 0.900 to 0.935g/cm ³Alathon, and the available ethene polymers requires to have comonomer so that density is brought down below 0.935g/cm among the present invention ³

Substantially linear ethylene polymers is the uniform polymeric with long chain branching.Long-chain branch has the comonomer distribution identical with polymer backbone and can have and polymer backbone length much at one.When using the ethene polymers of substantial linear in practice of the present invention, being characterized as of this polymkeric substance has the polymer backbone that per 1000 carbon atoms are replaced by 0.1 to 3 long-chain branch.

For quantitative determination process, referring to for example United States Patent (USP) 5,272,236 and 5,278,272; Randall (Rev.Macromo1.Chem.Phys., C29 (2﹠amp; 3), p.285-297), it has been discussed by using ¹³The C nuclear magnetic resonance spectroscopy(NMR spectroscopy) is measured long chain branching, Zimm, G.H. and Stockmayer, W.H.J.Chem.Phys., 17,1301 (1949); And Rudin, A., ModemMethods of Polymer Characterization, John Wiley ﹠amp; Sons, New York (1991) pp.103-112, its discussed use and low angle laser light scattering detector bonded gel permeation chromatography (" GPC-LALLS ") and with differential viscosity meter detector bonded gel permeation chromatography (" GPC-DV ").

Evenly line style or substantially linear ethylene polymers are the interpolymers of ethene and at least a alpha-olefin.When preparation ethylene propylene diene terpolymers (" EPDM ' s "), diene typically is the non-conjugated diene that contains 6 to 15 carbon atoms.The representative example that can be used for preparing the suitable non-conjugated diene of terpolymer comprises:

(a) straight chain aliphatics diene, for example 1, the 4-hexadiene; 1, the 5-heptadiene; With 1, the 6-octadiene;

(b) side chain aliphatics diene, 5-methyl isophthalic acid for example, 4-hexadiene; 3,7-dimethyl-1,6-octadiene; With 3,7-dimethyl-1,7-octadiene;

(c) the alicyclic diene of monocycle, for example 4 vinyl cyclohexene; 1-allyl group-4-isopropylidene hexanaphthene; 3-allyl group cyclopentenes; 4-allyl group tetrahydrobenzene; With the different propenyl of 1--4-butenyl tetrahydrobenzene;

(d) alicyclic the condensing and bridged ring diene, for example Dicyclopentadiene (DCPD) of many rings; Alkenyl, alkylidene group, cycloalkenyl group and ring alkylidene group norbornylene, for example 5-methylene-2-norbornene; 5-methylene radical-6-methyl-2-norbornylene; 5-methylene radical-6,6-dimethyl-2-norbornylene; 5-propenyl-2-norbornylene; 5-(3-cyclopentenyl)-2-norbornylene; 5-ethylidene-2-norbornene; 5-cyclohexylene-2-norbornylene; Or the like.

Preferred diene is selected from 1, the 4-hexadiene; Dicyclopentadiene (DCPD); 5-ethylidene-2-norbornene; 5-methylene-2-norbornene; The 7-methyl isophthalic acid, the 6-octadiene; 4 vinyl cyclohexene; Or the like.Operable a kind of preferred conjugated diolefine is a piperylene.

Most preferably ethene and at least a C ₃-C ₃₀The interpolymer of alpha-olefin (for example propylene, iso-butylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene alkynes and 1-octene), most preferably ethene and at least a C ₄-C ₂₀Alpha-olefin, particularly most preferably at least a C ₇-C ₃₀The interpolymer of alpha-olefin.

The be evenly distributed SCBDI or the CDBI of interpolymer of used narrow composition is that density (and being molecular weight on than low degree) is dependent among the present invention.Be lower than 0.898g/cm for density ³Polymkeric substance, CDBI value (as United States Patent (USP) 5,548, in 014 define) is lower than 70%.For density more than or equal to 0.898g/cm ³Interpolymer, CDBI value (as United States Patent (USP) 5,548, in No. 014 define) is more than or equal to 70%.

Used uniform copolymers is the uniform polymeric of ethene and at least a ethylenically unsaturated monomers, conjugation or non-conjugated diene, polyenoid etc. among the present invention.

Can use the linear ethylene/alpha-olefin interpolymer of polymerization that even short-chain branched distribution can be provided (as Elston at United States Patent (USP) 3,645, described in 992) the even branching of preparation.In its polymerization, Elston has used solvable vanadium catalyst system to make these polymkeric substance.Yet other companies such as Mitsui Petrochemical Company and Exxon Chemical Company have used so-called single-point metallocene catalyst system to make the polymkeric substance with even linear structure.Mitsui Petrochemical Company is with trade(brand)name " TAFMER at present ^TM" and Exxon Chemical Company with trade(brand)name " EXACT ^TM" the even line style ethylene/alpha-olefin interpolymer of supply.

The ethylene/alpha-olefin interpolymer of substantial linear can be available from the AFFINITY of Dow Chemical Company ^TMPolyolefin plastomers.The ethylene alpha-olefin interpolymers of substantial linear can be according to United States Patent (USP) 5,272, and the technology described in No. 5,278,272, No. 236 and the United States Patent (USP) is prepared, and the full content of these two patents all is incorporated herein by this reference.

The present invention is the polymer composition of a kind of derived from ethylene and alpha-olefin, and described composition can be used for substituting the traditional hot fusibleness tackiness agent that is used for bonding subsequently, and said composition also has and the similar binding property of tackiness agent that contains polymkeric substance, wax and tackifier.

The inventor has been found that the uniform copolymers that uses particular type can unexpectedly use separately or is used in combination with tackifier and makes commercial acceptable hot-melt adhesive.The present invention is a kind of hot-melt adhesive that contains specific synthetic interpolymer, when described interpolymer when suitable tackifier combine, can be used as the substitute of the hot-melt adhesive formulation that contains three components (wax, polymkeric substance and tackifier) mixture.

The uniform copolymers that uses in the hot-melt adhesive formulation of the present invention can use United States Patent (USP) 5,064,802,5,132,380,5,703,187,6,034,021, the Preparation of Catalyst of disclosed qualification geometrical shape among EP 0 468 651, EP 0 514 828, WO93/19104 and the WO95/00526, these patents all are incorporated herein by this reference.Another kind of appropriate catalyst is a United States Patent (USP) 5,044,438; 5,057,475; Disclosed metalloscene catalyst in 5,096,867 and 5,324,800, these patents all are incorporated herein by this reference.It is to be noted that the catalyzer that limits geometrical shape can be considered as metalloscene catalyst, both are called single-point catalyst sometimes in this field.

For example, catalyzer can be selected from the metal coordination complex that meets following general formula:

General formula I

Wherein: M is the periodic table of elements 3, the metal of 4-10 family or lanthanon; Cp ^*Be with η ⁵The cyclopentadienyl of keyed jointing pattern and M keyed jointing or substituted cyclopentadienyl; Z contains boron, or the part of element of periodic table of elements family 14 and optional sulphur or oxygen, and this part contains maximum 40 non-hydrogen atoms, and randomly, Cp ^*Form the fused rings system together with Z; All be the anion ligand group independently under every kind of situation of X, described X contains maximum 30 non-hydrogen atoms; When Y was anionic, n lacked 2 than the valence number of M, and when Y was neutrality, n lacked 1 than the valence number of M; L is the neutral Lewis base ligands group in each case independently, and described L contains maximum 30 non-hydrogen atoms; M is 0,1,2,3 or 4; And Y is and the anionic or the neutral ligand group of Z and M keyed jointing that Y comprises nitrogen, phosphorus, oxygen or sulphur and contain maximum 40 non-hydrogen atoms that randomly Y and Z form the fused rings system together.

Appropriate catalyst can also be selected from the metal coordination complex that meets following general formula;

Wherein R ' is independently selected from hydrogen, alkyl, aryl, silyl, germyl, cyano group, halogen or their mixture that contains maximum 20 non-hydrogen atoms in each case; X is independently selected from hydride, halogen, alkyl, aryl, silyl, germyl, aryloxy, alkoxyl group, acid amides, siloxy-or their mixture that contains maximum 20 non-hydrogen atoms in each case; L is in each case independently for containing the neutral Lewis base ligands of maximum 30 non-hydrogen atoms; Y is-O-,-S-,-NR ^*-,-PR ^*-or be selected from OR ^*, SR ^*, NR ^* ₂, PR ^* ₂Neutral two-electron donor part; M, n and m are as defined above; Z is SIR ^* ₂, CR ^* ₂, SiR ^* ₂SiR ^* ₂, CR ^* ₂CR ^* ₂, CR ^*=CR ^*, CR ^* ₂SiR ^* ₂, GeR ^* ₂, BR ^*, BR ^* ₂Wherein: R ^*All be independently selected from the hydrogen, alkyl, aryl, silyl, haloalkyl, halogenated aryl or their mixture that contain maximum 20 non-hydrogen atoms in each case, perhaps from Y, two or more R of Z ^*Group, or Y and Z form the fused rings system together.

Should be noted that although formula I and following formula show the monomer structure of catalyzer, complex compound can also exist as dipolymer or higher oligopolymer.

Further preferably, R ', Z or R ^*In at least one is to electronic section.Therefore, extremely preferably, Y be general molecular formula-N (R " ")-or-P (R " ")-the group of nitrogenous or phosphorus, R wherein " " be C _1-10Alkyl or aryl, just amido or phosphido.

Other catalyzer can be selected from the amido silane that meets following general formula-or amido alkane two bases-compound:

Wherein: M is with η ⁵The titanium of keyed jointing pattern and cyclopentadienyl keyed jointing, zirconium or hafnium; R ' is independently selected from hydrogen, silyl, alkyl, aryl or their mixture that contains maximum 10 carbon or Siliciumatom in each case; E is silicon or carbon; X is in each case independently for containing hydride, halogen, alkyl, aryl, aryloxy or the alkoxyl group of maximum 10 carbon atoms; M is 1 or 2; N is 1 or 2 according to the valency of M.

The example of above-mentioned metal complex includes but not limited to following compound, and promptly wherein the R ' on the amido is methyl, ethyl, propyl group, butyl, amyl group, hexyl, (comprising isomer), norcamphyl, benzyl, phenyl or the like; Cyclopentadienyl be cyclopentadienyl, indenyl, tetrahydro indenyl, fluorenyl, octahydrofluorenyl, or the like; R ' on the aforementioned cyclopentadienyl is hydrogen, methyl, ethyl, propyl group, butyl, amyl group, hexyl, (comprising isomer), norcamphyl, benzyl, phenyl or the like in each case; And X is chloro-, bromo-, iodo-, methyl, ethyl, propyl group, butyl, amyl group, hexyl, (comprising isomer), norcamphyl, benzyl, phenyl or the like.

Particular compound includes but not limited to, (dimethyl) (tertiary butyl amido) (tetramethyl--η ⁵-cyclopentadienyl)-1,2-second two basic zirconiums, (dimethyl) (tertiary butyl amido) (tetramethyl--η ⁵-cyclopentadienyl)-1,2-second two basic titaniums, dichloride (methyl amido) (tetramethyl--η ⁵-cyclopentadienyl)-1,2-second two basic zirconiums, dichloride (methyl amido) (tetramethyl--η ⁵-cyclopentadienyl)-1,2-second two basic titaniums, dichloro (ethyl amido) (tetramethyl--η ⁵-cyclopentadienyl)-methylene radical titanium, dibenzyl (tertiary butyl amido) phenylbenzene (tetramethyl--η ⁵-cyclopentadienyl)-silane zirconium, dichloride (benzyl amido) dimethyl-(tetramethyl--η ⁵-cyclopentadienyl)-silane titanium, dibenzyl (phenyl phosphido) dimethyl (tetramethyl--η ⁵-cyclopentadienyl) silane zirconium etc.

Another kind of appropriate catalyst is as US 5,965,756 and US 6,015,868 in the disclosed metal complex that contains substituted indenyl, their full content is incorporated herein by this reference.Other catalyzer is disclosed in the application of common pending trial: U.S. Patent application 09/230,185 and 09/715,380, and U.S. Provisional Application 60/215,456,60/170,175 and 60/393,862.The disclosed full content of all patent applications formerly all is incorporated herein by this reference.These catalyzer tend to have higher molecular weight.

One class of above-mentioned catalyzer is the metal that contains indenyl, wherein:

M be have+2 ,+3 or+titanium, zirconium or the hafnium of 4 positive oxidation state;

A ' is at least 2 or 3 substituted indenyls, substituting group is selected from alkyl, fluorine substituted hydrocarbon radical, the alkyl that-oxyl replaces, the alkyl that dialkyl amido replaces, alkyl, silyl, germyl and their mixture that dialkyl amido replaces, described substituting group contains maximum 40 non-hydrogen atoms, and A ' is further by divalence Z group and M covalency keyed jointing; Z is that Z comprises boron by the divalent moiety of σ-key and A ' and M keyed jointing, or the element of the periodic table of elements 14 families, also comprises nitrogen, phosphorus, sulphur or oxygen; X is anionic that contains maximum 60 atoms or the dual anion type ligand groups except that this class part of ligand groups of cyclic, delocalized, π-key bonding; X ' is in each case independently for containing the neutral Lewis base of maximum 20 atoms; P is 0,1 or 2, and littler by 2 than the positive oxidation state of M, and condition is when X is the dual anion type ligand groups, and p is 1; And q is 0,1 or 2.

Above-mentioned complex compound can exist with the segregation crystal of optional respective pure form or as (choosing wantonly in solvent with the form of solvation adducts with the mixture of other complex compound, especially in the organic liquid), and with the form of dipolymer or its chelating derivative (wherein sequestrant is an organic materials, preferred neutral Lewis base, especially trialkylamine, trihydrocarbyl phosphine or its halide derivative) exist.

Preferred catalyzer is the complex compound that meets following general formula:

R wherein ₁And R ₂For being selected from alkyl, silyl, germyl or their mixture of hydrogen, alkyl, perfluor replacement, described group contains maximum 20 non-hydrogen atoms to group independently, and condition is R ₁Or R ₂In at least one is not a hydrogen; R ₃, R ₄, R ₅And R ₆For being selected from alkyl, silyl, germyl or their mixture of hydrogen, alkyl, perfluor replacement, described group contains maximum 20 non-hydrogen atoms to group independently; M is titanium, zirconium or hafnium; Z contains the element of boron or periodic table of elements family 14 and the divalent moiety that also contains nitrogen, phosphorus, sulphur or oxygen, and this part contains maximum 60 non-hydrogen atoms; P is 0,1 or 2; Q is 0 or 1; Condition is: when p is 2, q is 0, M is in+4 positive oxidation state, and X is the anionic part, be selected from halogenide, alkyl,-oxyl, two (alkyl) amido, two (alkyl) phosphorus (phosphido), alkyl sulphur (sulfido) and silyl and their halogen-, two (alkyl) are amino-,-oxyl-and the derivative of two (alkyl) phosphino--replacement, the X group contains maximum 20 non-hydrogen atoms; When p is 1, q is 0, M is in+3 positive oxidation state, and X is a stabilization anionic ligand groups, is selected from allyl group, 2-(N, N-dimethylaminomethyl) phenyl and 2-(N, the N-dimethyl)-aminobenzyl, or M is in+4 positive oxidation state, and X is the divalent derivative of conjugated diolefine, and M and X constitute metal ring amylene group together; And when p was 0, q was 1, and M is in+2 positive oxidation state, and X ' is neutral conjugation or non-conjugated diene, was optionally replaced by one or more alkyl, and X ' contains maximum 40 carbon atoms and forms π-complex compound with M.

Wherein: R ₁And R ₂Be hydrogen or C _1-6Alkyl, condition are R ₁Or R ₂In at least one is not a hydrogen; R ₃, R ₄, R ₅And R ₆Be hydrogen or C independently _1-6Alkyl; M is a titanium; Y is-O-,-S-,-NR ^*-,-PR ^*-; Z is SiR ^* ₂, CR ^* ₂, SiR ^* ₂SiR ^* ₂, CR ^* ₂CR ^* ₂, CR ^*=CR ^*, CR ^* ₂SiR ^* ₂Or GeR ^* ₂R ^*In each case all independently for hydrogen or for being selected from a member in alkyl,-oxyl, silyl, haloalkyl, halogenated aryl or their mixture, R ^*Contain maximum 20 non-hydrogen atoms, and randomly, from two R of Z ^*Group (is worked as R ^*When being not hydrogen) or from the R of Z ^*Group with from the R of Y ^*Group forms member ring systems; P is 0,1 or 2; Q is 0 or 1; Condition is: when p was 2, q was 0, and M is in+4 positive oxidation state, and X is methyl or benzyl in each case independently; When p was 1, q was 0, and M is in+3 positive oxidation state, and X is 2-(N, a N-dimethyl) aminobenzyl; Or M is in+4 positive oxidation state, and X is 1, the 4-butadienyl; When p was 0, q was 1, and M is in+2 positive oxidation state, and X ' is 1,4-phenylbenzene-1,3-butadiene or 1,3-pentadiene.A kind of diene in back has been represented asymmetric diene group, and it can be made and be actually the metal complex of the mixture of geometrical isomer separately.

The catalyzer that other can use in practice of the present invention disclosed herein, promotor, catalyst system, be included in those disclosed in the following document with activating technology: United States Patent (USP) 5,616,664, on August 1st, 1996 disclosed WO 96/23010, on March 25th, 1999 disclosed WO 99/14250, on September 24th, 1998 disclosed WO 98/41529, on November 13rd, 1997 disclosed WO 97/42241, on November 13rd, 1997 disclosed WO97/42241, by people such as Scollard at J.Am.Chem.Soc1996,118, those disclosed content among the 10008-10009, on November 13rd, 1996 disclosed EP 0 468 537 B1, on June 26th, 1997 disclosed WO 97/22635, on October 13rd, 1999 disclosed EP 0 949278 A2, on October 13rd, 1999 disclosed EP 0 949 279 A2, on December 27th, 2000 disclosed EP 1 063 244 A2, United States Patent (USP) 5,408,017, United States Patent (USP) 5,767,208, United States Patent (USP) 5,907,021, on August 11st, 1988 disclosed WO 88/05792, on August 11st, 1988 disclosed WO 88/05793, on December 23rd, 1993 disclosed WO 93/25590, United States Patent (USP) 5,599761, United States Patent (USP) 5,218,071, July 12 nineteen ninety disclosed WO 90/07526, United States Patent (USP) 5,972,822, United States Patent (USP) 6,074,977, United States Patent (USP) 6,013,819, United States Patent (USP) 5,296,433, United States Patent (USP) 4,874,880, United States Patent (USP) 5,198,401, United States Patent (USP) 5,621,127, United States Patent (USP) 5,703,257, United States Patent (USP) 5,728,855, United States Patent (USP) 5,731,253, United States Patent (USP) 5,710,224, United States Patent (USP) 5,883,204, United States Patent (USP) 5,504,049, United States Patent (USP) 5,962,714, United States Patent (USP) 5,965,677, United States Patent (USP) 5,427,991, on October 28th, 1993 disclosed WO93/21238, on February 17th, 1994 disclosed WO 94/03506, on October 28th, 1993 disclosed WO 93/21242, on January 6th, 1994 disclosed WO94/00500, on January 4th, 1996 disclosed WO 96/00244, on November 12nd, 1998 disclosed WO 98/50392; People such as Wang, Organometallics 1998,17,3149-3151; People such as Younkin, Science 2000,287,460-462; Chen and Marks, Chem.Rev.2000,100,1391-1434; Alt and Koppl, Chem.Rev.2000,100,1205-1221; People such as Resconi, Chem.Rev.2000,100,1253-1345; People such as Ittel, Chem.Rev.2000,100,1169-1203; Coates, Chem.Rev.2000,100,1223-1251; On May 9th, 1996 disclosed WO 96/13530; The full content of all these patents and publication all is incorporated herein by this reference.Same available is disclosed catalyzer, promotor and a catalyst system in following document: the USSN 09/230,185 that on January 15th, 1999 submitted to; United States Patent (USP) 5,965,756; United States Patent (USP) 6,150,297; The USSN 09/715,380 that on December 17th, 2000 submitted to; The full content of all these patents and publication all is incorporated herein by this reference.In addition, for example at United States Patent (USP) 6,015, described the method for preparing aforementioned catalyzer in 868, its full content is incorporated herein by this reference.

Promotor:

Can be by combining with active cocatalyst or making above-mentioned catalyzer produce catalytic activity by activating technology.The active cocatalyst that available is suitable includes but not limited to herein, polymeric or oligomeric aikyiaiurnirsoxan beta (alumoxanes), especially methylaluminoxane, the methylaluminoxane of triisobutyl aluminium modification, or isobutyl aluminium alkoxide; Neutral lewis acid, for example C _1-3013 compounds of group that alkyl replaces, especially three (alkyl) aluminium-or three (alkyl) boron compounds and halo (comprising perhalogeno) derivative thereof, in each alkyl or halo alkyl, contain 1 to 30 carbon, more particularly perfluoro three (aryl) boron and perfluoro three (aryl) aluminum compound, fluoro-replaces (aryl) boron compound and the mixture that contains the aluminum compound of alkyl, especially the mixture of three (pentafluorophenyl group) borines and trialkylaluminium, or the mixture of three (pentafluorophenyl group) borine and alkylaluminoxanes, the mixture of three (pentafluorophenyl group) borines and methylaluminoxane more particularly, with the mixture of three (pentafluorophenyl group) borine, be more particularly three (pentafluorophenyl group) borines and three (pentafluorophenyl group) aluminium with the methylaluminoxane (MMAO) of the more senior alkyl modification of using certain percentage; Non-polymeric, compatible, non-coordinate, formation ionic compound (be included in and use this compounds under the oxidizing condition), especially use compatible, anionic ammonium-, Phosphonium of non-coordinate-, oxygen-, carbonium-, silyl (silylium)-or sulfonium-salt, or compatible, the anionic ferrocene of non-coordinate (ferrocenium) salt; (bulk) electrolysis of the body of aforementioned active cocatalyst and technology and mixture.In following reference, aforementioned active cocatalyst and activating technology: EP-A-277 has been described for different metal complexs before, 003, US-A-5,153,157, US-A-5,064,802, EP-A-468,651 (being equivalent to US07/547,718), EP-A-520,732 (are equivalent to US 07/876,268) and EP-A-520732 (being equivalent to the U S07/884 that submitted on May 1st, 1992,966).Formerly patent or the disclosed full content of patent application all are incorporated herein by this reference for all.

The mixture of neutral lewis acid, especially contain the mixture that contains halo three (alkyl) boron compound (especially three (pentafluorophenyl group) borine) of 1 to 20 carbon in the trialkyl aluminium compound of 1 to 4 carbon and each alkyl in each alkyl, and the mixture of the mixture of these neutral lewis acid mixtures and polymeric or oligomeric aikyiaiurnirsoxan beta and single neutral lewis acid (especially three (pentafluorophenyl group) borine) and polymerization or oligomeric aikyiaiurnirsoxan beta is particularly desirable active cocatalyst.Also observe, when the amount of aikyiaiurnirsoxan beta reduces, use this three (pentafluorophenyl group) borine/aikyiaiurnirsoxan beta mixture to produce the most effective catalyst activation effect.4 family's metal complexs: three (pentafluorophenyl group) borine: the preferred molar ratio of aikyiaiurnirsoxan beta is 1:1:1 to 1:5:10, more preferably 1:1:1 to 1:3:5.This efficient use of the aikyiaiurnirsoxan beta of low amount can enable to have with the aluminoxane catalyst manufacturing of less costliness the olefin polymer of high catalytic efficiency.In addition, can obtain lower and so the more transparent polymkeric substance of aluminium residual volume.

In some embodiments of the present invention, the suitable ion that can be used as promotor forms compound and comprises as the positively charged ion of the Bronsted acid that can give electronics and compatible non-coordination anion A ^-Term used herein " non-coordination " is meant not can be with the precursor complexes that contains 4 family's metals and by its deutero-catalysis derivative coordinate negatively charged ion or material coordination, or only still enough is easy to by neutral Lewis base metathetical negatively charged ion or material thus with these complex compound coordinations very weakly.Non-coordination anion refers in particular to following negatively charged ion, promptly when in cationic metal complex, being used as the charge balance negatively charged ion, its anion substituent or fragment can not transferred on the positively charged ion to form neutral complex in this process, described this neutral complex can disturb the desired use of cationic metal complex as catalyzer to a great extent." compatible negatively charged ion " is meant following negatively charged ion, promptly when the initial complex compound that forms decomposes non-degradable for neutral and can not disturb subsequently polymerization or other desirable application of complex compound.

Preferred anionic surfactants is to contain single co-ordination complex those negatively charged ion of (comprising charged metal or metalloid core), this negatively charged ion can be equilibrated at two kinds of components in conjunction with the time active catalyst class (metallic cation) that may form electric charge.Similarly, this negatively charged ion should enough be easy to by alkene formula, diolefin formula and acetylene formula unsaturated compound or other neutral Lewis base (for example ether or nitrile) displacement.Suitable metal includes, but not limited to aluminium, gold and platinum.Suitable metalloid includes, but not limited to boron, phosphorus and silicon.Contain the compound of negatively charged ion (this negatively charged ion comprises the co-ordination complex that contains single metal or metalloid atom) yes known in the art, and many, particularly this compound that contains single boron atom at anionicsite is commercially available.

Preferred this promotor can be expressed as following general formula:

(L ^*-H) _d ⁺(A) ^d-

General formula VII

L wherein ^*It is neutral Lewis base; (L ^*-H) ⁺It is Bronsted acid; (A) ^D-Be that electric charge is the negatively charged ion of d-, d is 1 to 3 integer.More preferably, A ^D-Meet formula: [M ' Q ₄] ^-, wherein M ' is+boron or the aluminium of 3 positive oxidation state; Q is independently selected from hydride, dialkyl group amido, halogenide, alkyl, hydrocarbyl oxide, halo alkyl, halo-oxyl, halo silyl alkyl (comprise perhalogeno alkyl-perhalogeno-oxyl-and perhalogeno silyl alkyl) in each case, Q contains maximum 20 carbon, and condition is that only to be no more than a place be Q halogenide.At United States Patent (USP) 5,296, the example of suitable hydrocarbyl oxide Q group is disclosed in 433.

In preferred specific embodiments, d is 1, that is to say, counter ion are single negative charges and are A ^-Can be expressed as following general formula to the useful especially boracic active cocatalyst of Preparation of Catalyst of the present invention:

(L ^*-H) ⁺(M’Q ₄) ^-

General formula VIII

L wherein ^*As mentioned above; M ' is that positive oxidation state is 3 boron or aluminium; Q is the alkyl, the-oxyl that contain maximum 20 carbon, fluoridizes alkyl, fluoridizes-oxyl or silyl fluoride base alkyl, and condition is that only to be no more than a place be the Q alkyl.Most preferably, Q is fluoro aryl in each case, especially is pentafluorophenyl group.Preferred (L ^*-H) ⁺Positively charged ion is N, accelerine, N, N-two (octadecyl) aniline, two (octadecyl) ammonium methyl, two (hydrogenation tallowyl) ammonium and the tributyl ammonium of methyl.

The example that can be used as the boron compound of active cocatalyst (is given an example, but be not limited to) be trisubstituted ammonium salt, for example: four (pentafluorophenyl group) boric acid trimethyl ammonium, four (pentafluorophenyl group) boric acid triethyl ammonium, four (pentafluorophenyl group) boric acid tripropyl ammonium, four (pentafluorophenyl group) boric acid, three normal-butyl ammoniums, four (pentafluorophenyl group) boric acid, three sec-butyl ammoniums, four (pentafluorophenyl group) boric acid N, accelerine, normal-butyl three (pentafluorophenyl group) boric acid N, accelerine, benzyl three (pentafluorophenyl group) boric acid N, accelerine, four (4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluoro phenyl) boric acid N, accelerine, four (4-(triisopropyl silyl)-2,3,5,6-tetrafluoro phenyl) boric acid N, accelerine, penta fluoro benzene oxygen base three (pentafluorophenyl group) boric acid N, accelerine, four (pentafluorophenyl group) boric acid N, the N-Diethyl Aniline, four (pentafluorophenyl group) boric acid N, N-dimethyl-2,4, the 6-trimethylaniline, four (2,3,4,6-tetrafluoro phenyl) boric acid TMA (TriMethylAmine), four (2,3,4,6-tetrafluoro phenyl) boron triethylenetetraminehexaacetic acid ammonium, four (2,3,4,6-tetrafluoro phenyl) boric acid 3 third ammoniums, four (2,3,4,6-tetrafluoro phenyl) boric acid three normal-butyl ammoniums, four (2,3,4,6-tetrafluoro phenyl) boric acid dimethyl (tertiary butyl) ammonium, four (2,3,4,6-tetrafluoro phenyl) boric acid N, accelerine, four (2,3,4,6-tetrafluoro phenyl) boric acid N, the N-Diethyl Aniline, and four (2,3,4,6-tetrafluoro phenyl) boric acid N, N-dimethyl-2; Dialkyl ammonium salt, for example: four (pentafluorophenyl group) boric acid two-(sec.-propyl) ammonium and four (pentafluorophenyl group) boric acid dicyclohexyl ammonium; San Qu Dai phosphonium salt, for example: four (pentafluorophenyl group) boric acid triphenyl phosphonium, four (pentafluorophenyl group) boric acid three (neighbour-tolyl) Phosphonium and four (pentafluorophenyl group) boric acid three (2,6-3,5-dimethylphenyl) Phosphonium; Two replace oxonium salt, for example: four (pentafluorophenyl group) boric acid diphenyloxide, four (pentafluorophenyl group) boric acid, two (o-tolyl) oxygen and four (pentafluorophenyl group) boric acid two (2, the 6-3,5-dimethylphenyl) oxygen; Two replace sulfonium salt, for example: four (pentafluorophenyl group) boric acid phenylbenzene sulfonium, four (pentafluorophenyl group) boric acid, two (neighbour-tolyl) sulfoniums and four (pentafluorophenyl group) boric acid two (2, the 6-3,5-dimethylphenyl) sulfonium.

Preferred silyl salt active cocatalyst includes but not limited to: four (pentafluorophenyl group) boric acid trimethyl silyl, four (pentafluorophenyl group) boric acid triethylsilyl and ether thereof replace adducts.Be disclosed in J.Chem.Soc.Chem.Comm.1993 prevailingly before the silyl salt, 383-384 and Lambert, people such as J.B., Organometallics, 1994,13, among the 2430-2443.The application as the active cocatalyst of addition polymerization catalyzer of above-mentioned silyl salt is disclosed in United States Patent (USP) 5,625, and in 087, its full content is incorporated herein by this reference.Some complex compound of alcohol, mercaptan, silanol and oxime and three (pentafluorophenyl group) borine also is effective catalyst activator and can be used in the specific embodiment of the present invention.These promotors are disclosed in United States Patent (USP) 5,296, and in 433, its full content also is incorporated herein by this reference.

Can in carry out the solvent that polymerization uses by the solution polymerization program, add essential component and prepare catalyst system as even catalyzer.Also can be by preparing catalyst system with must component being adsorbed on the catalyst support material (for example silica gel, aluminum oxide or other suitable inorganic carrier material) and used as heterogeneous catalyst.When preparing, preferably use silica supported material with heterogeneous or supported form.

Whenever, each composition and catalyst component all should be avoided oxygen and moisture.Therefore, catalyst component and catalyzer should preparation and recovery under the environment of anaerobic and no moisture.Therefore, preferably, be reflected at and exist dry inert gas for example to carry out under the environment of nitrogen or argon gas.

Metal complex: the mol ratio of used active cocatalyst is preferably 1:1000 to 2:1, more preferably 1:5 to 1.5:1, most preferably 1:2 to 1:1.Under this preferred situation with the methylaluminoxane activated metal complex compound of three pentafluorophenyl group borines or triisobutyl aluminium modification, titanium: boron: the mol ratio of aluminium is generally 1:10:50 to 1:0.5:0.1, is typically about 1:3:5 most.

Generally speaking, finish polymerization under the condition that is used for Z-N or Kaminsky-Sinn type polyreaction, just, reactor pressure is normal atmosphere to 3500 normal atmosphere (34.5 kPas).Temperature of reactor should be higher than 80 ℃, is generally 100 ℃ to 250 ℃, is preferably 100 ℃ to 150 ℃, uses higher temperature of reactor, just is higher than the formation that 100 ℃ temperature of reactor helps the lower molecular weight polymkeric substance usually.

Usually, with 10 to 1000psi (70 to 7000 kPas), most preferably the ethene differential pressure of 40 to 60psi (300 to 400 kPas) is carried out polymerization.Polymerization is usually at 80 to 250 ℃, preferred 90 to 170 ℃, most preferably is higher than under 95 to 160 ℃ the temperature and carries out.

In most of polyreactions, catalyst system therefor: the mol ratio of polymerizable compound is 10 ^-12: 1 to 10 ^-1: 1, more preferably 10 ^-9: 1 to 10 ^-5: 1.

Solution polymerization condition has adopted a kind of solvent that is applicable to each component of reaction.Preferred solvent is included in and is the mineral oil of liquid and various hydrocarbon under the temperature of reaction.The illustrative example of useable solvents comprises alkane, for example pentane, iso-pentane, hexane, heptane, octane and nonane, and comprise kerosene and Isopar E ^TMAt interior alkane mixture (available from Exxon Chemicals Inc.); Cycloalkanes, for example pentamethylene and hexanaphthene; And aromatic substance, for example benzene,toluene,xylene, ethylbenzene and diethylbenzene.

The amount of described solvent is for being enough to prevent being separated in the reactor.Because solvent plays the effect that absorbs heat, less solvent produces more not adiabatic reactor.Solvent: ethene ratio (weight basis) is generally 2.5:1 to 12:1, exceeds this scope and can damage catalyst efficiency.Most typical solvent: ethene ratio (weight basis) is 5:1 to 10:1.

Polymerization can be undertaken by polymerization in batches or continuously, and the polymkeric substance of preparation substantial linear requires to use continuous polymerization.In continuous processing, ethene without interruption, comonomer and optional solvent and diene and from reactor, be continuously removed polymer product in reaction zone.

B) tackifier component

Need to add tackifier so that can be bonding before tackiness agent solidifies or hardens.Its example is the operation of high speed cereal joint sealing, and wherein at the thermosetting adhesive solidified simultaneously, the overlap joint capping of chest needs adhesion mutually.

Can be used for tackifying resin of the present invention and comprise aliphatic series, alicyclic and aromatic hydrocarbon and modification hydrocarbon and hydrogenated form; Terpene and modification terpene and hydrogenated form; With rosin and rosin derivative and hydrogenated form; And their mixture.These tackifying resins have 70 ℃ to 150 ℃ ring and ball softening point, and have the viscosity (using brookfield's viscometer to measure) that is no more than 2000 centipoises usually under 350 ℉ (177 ℃).They can have different hydrogenation degrees, or saturation ratio (this is another Essential Terms).The available example comprises available from Kingsport, the Eastotac of the EastmanChemical Co. of Tenn. ^TMH-100, H-115 and H-130, it is partially hydrogenated alicyclic petroleum hydrocarbon resin, softening temperature is respectively 100 ℃, 115 ℃ and 130 ℃.Can be respectively purchase with E level, R level, L level and W level, these show different hydrogenation degrees, and E is that hydrogenation degree is minimum, and W is that hydrogenation degree is the highest.The bromine number that the E level has is 15, and the bromine number that the R level has is 5, and the bromine number that the L level has is 3, and the bromine number that the W level has is 1.Eastotac from Eastman ChemicalCo. ^TMH-142R has about 140 ℃ softening temperature.Other available tackifying resin comprises all can be available from Houston, the Escorez of the Exxon Chemical Co. of Tex ^TM5300,5400 and 5637, partially hydrogenated alicyclic petroleum hydrocarbon resin, and Escorez ^TM5600, partially hydrogenated aromatic modified petroleum hydrocarbon resin; Wingtack ^TMExtra, it is can be available from Akron, aliphatic series, the aromatics petroleum hydrocarbon resin of the Goodyear Chemical Co. of Ohio; Hercolite ^TM2100, can be available from Wilmington, the Hercules of Del., the partially hydrogenated alicyclic petroleum hydrocarbon resin of Inc..

Rosin with different hydrogenation degrees and modified rosin that many types are arranged comprise gum resin (gum rosins), wood rosin, starex, distillation rosin, dimerization colophonium and polymerized rosin.Some concrete modified rosins comprise the glycerine and the pentaerythritol ester of wood rosin and starex.Commercially available grade includes but not limited to, Sylvatac ^TM1103, a kind of can be available from the rosin pentaerythritol ester of ArizonaChemical Co.; Unitac ^TMR-100Lite, a kind of can be available from Wayne, the rosin pentaerythritol ester of the Union Camp of N.J.; Permalyn ^TM305, a kind of can be available from the tetrahydroxybutane innovation wood rosin of Hercules; And Foral 105, its be a kind of equally can be available from the highly hydrogenated rosin pentaerythritol ester of Hercules.Sylvatac ^TMR-85 and 295 is can be available from the sylvic acid of 85 ℃ and the 95 ℃ fusing points of Arizona Chemical Co., Foral AX be a kind of can be available from Hercules, the hydroabietic acid of 70 ℃ of fusing points of Inc.NirezV-2040 be a kind of can be available from the phenol modified terpene resin of Arizona Chemical Co..

The tackifier that another is exemplary, Piccotac 115, have the viscosity of about 1600 centipoises under 350 ℉ (177 ℃).Other typical tackifier have the viscosity far below 1600 centipoises, for example 50 to 300 centipoises under 350 ℉ (177 ℃).

Exemplary aliphatic resin comprises those that supply with following trade(brand)name: Escorez ^TM, Piccotac ^TM, Mercures ^TM, Wingtack ^TM, Hi-Rez ^TM, Quintone ^TM, Tackirol ^TMDeng.Exemplary polyterpene resin comprises those that supply with following trade(brand)name: Nirez ^TM, Piccolyte ^TM, Wingtack ^TM, Zonarez ^TMDeng.Exemplary hydrogenated resin comprises those that supply with following trade(brand)name: Escorez ^TM, Arkon ^TM, Clearon ^TMDeng.Exemplary blended aliphatic-aromatic resin comprises Escorez ^TM, Regalite ^TM, Hercures ^TM, AR ^TM, Imprez ^TM, Norsolene ^TMM, Marukarez ^TM, Arkon ^TMM, Quintone ^TMDeng.These tackifier can use with polymkeric substance of the present invention, as long as they use on compatible degree.Can use other tackifier, as long as they are with evenly line style or substantial linear ethylene/alpha-olefin interpolymer are compatible.

In some application of the present invention, wish sometimes not use tackifier or prepare hot-melt adhesive with minimum tackifier.Because the tackifier foul smelling, therefore etching mechanism equipment and can not separating with circulation paper pulp easily easily reduce as far as possible that to use the hot-melt adhesive of tackifier be favourable.In addition, because tackifier can be degraded under high-temperature usually, reduce as far as possible and use the hot-melt adhesive of tackifier to show the thermostability of raising.

Can characterize the tackifier that are added in the hot-melt adhesive with the parameter of softening temperature, proportion or acid number and so on.Tackifier can be selected from aforesaid various tackifier, but are not limited to this, and the acid number that can be selected from certain limit is the tackifier of feature, and for example acid number is 0 to 100, more preferably 0 to 25.8 tackifier, and most preferably acid number is the tackifier of 3-10.

C) other additive

Tackiness agent comprises tackiness agent of the present invention, can also contain many annexing ingredients, for example stablizer, softening agent, weighting agent or antioxidant.Stablizer applicatory that can comprise in binder composition of the present invention or antioxidant are high molecular weight hindered phenols and multifunctional phenol, for example sulfur-bearing and phosphorated phenol.Hindered phenol well known by persons skilled in the art can be described as following phenolic compound, its contain near the phenolic hydroxyl group have living space on very big group.Particularly, usually the tertiary butyl at least one ortho position at phenolic hydroxyl group is substituted onto on the phenyl ring.Very big substituted radical can be used for blocking its stretching frequency near these spaces of the existence hydroxyl, and correspondingly blocks its reactivity.This just steric hindrance provides the stability of these phenolic compounds.

Representational hindered phenol includes but not limited to: 2,4, and 6-trialkyl mono-hydroxy phenol; 1,3,5-trimethylammonium-2,4,6-three-(3,5-two-tertiary butyl-4-hydroxy benzyl)-benzene; Four-3 (3, the 5-di-tert-butyl-hydroxy phenyl)-propionic acid pentaerythritol esters can be with trade mark

1010 buy; Octadecane base-3 (3, the 5-di-tert-butyl-hydroxy phenyl)-propionic ester; 4,4 '-methylene-bis (4-methyl-6-tert butyl-phenol); 4,4 '-thiobis (the 6-tertiary butyl-ortho-cresol); 2,6 di t butyl phenol; 6-(4-hydroxyphenoxy)-2, two (n-octyl-sulfo-)-1,3 of 4-, 5 triazines; 3,5-di-t-butyl-4-hydroxy-benzoic acid 2-(n-octyl sulfo-) ethyl ester; 3,5-di-t-butyl-4-hydroxyl-benzylphosphonic acid two-Octadecane base ester; With six (3,3,5-di-t-butyl-4-hydroxyl-phenyl) propionic acid sorbitol ester.

Antioxidant includes but not limited to butylated hydroxyanisol (" BHA ") or Yoshinox BHT (" BHT "), and described oxygenant also can be used for making the thermostability of formulation higher.The add-on of these stablizers and antioxidant is about 0.01% to about 5% of a formulation weight.

Use known synergist can further improve the performance of these antioxidants with antioxidant.Some known synergists are, for example, and thiodipropionate and phosphoric acid salt.Also can use sequestrant and metal passivator.The example of these compounds comprises ethylenediamine tetraacetic acid (EDTA) (" EDTA "), its salt more preferably, and double salicylaldehyde propylene diamine.Especially available is a distearyl thiodipropionate.In the time of in adding binder composition, the amount of these stablizers (if with) is typically about 0.1 to about 1.5wt%, and more preferably about 0.25 to about 1.0wt%.

The application also considers polymeric additive is added in the tackiness agent.Polymeric additive is selected from and contains the 10 ethylene methyl acrylate polymkeric substance to the 28wt% methyl acrylate; Acid number is 25 to 150 ethylene acrylic acid co polymer; Polyethylene; Polypropylene; Poly-(butene-1-altogether-ethene) polymkeric substance, and the ethylene n-butyl acrylate copolymer of lower molecular weight and/or low-melt-index.When adding this type of polymeric additive, its amount mostly is about 15wt% of composition weight most.

According to the expection end-use of binder composition, can comprise that routine is added to other additive such as softening agent, pigment and dyestuff in the hot-melt adhesive.In addition, (accessory) tackifier and/or the wax that append on a small quantity that can also in formulation of the present invention, add a small amount of (just at most about 10wt%), for example synthetic wax of Microcrystalline Wax, hydrogenated castor oil, styrene-ethylene butylstyrene (SEBS) resin and vinyl acetate modified.Can use softening agent to replace the secondary tackifier or use to improve viscosity and to improve the viscosity of binder composition with the secondary tackifier.

Can in these compositions, add dispersion agent.Dispersion agent can be following chemical---composition is for example being disperseed from the surface of having used this dispersion agent in the water surrounding.Dispersion agent also can be following reagent---composition is disperseed from the surface of having used this dispersion agent.Such as is known to persons skilled in the art, the example of these dispersion agents comprises tensio-active agent, emulsifying agent and various positively charged ion, negatively charged ion or non-ionic dispersing agent.The example of cation dispersing agent is amine, acid amides and derivative thereof.Soap, acids, ester class and alcohols belong to known anionic dispersing agents.Dispersion agent add the recovery property again that affiliation influence scribbles the product of hot-melt adhesive.

Tensio-active agent can be selected from various known tensio-active agents.It can comprise non-ionic compound, for example the ethoxylate that can buy.Example comprises fatty alcohol ethoxylate, alkylamine ethoxylate, alkylphenol ethoxylate, octylphenol ethoxylate etc.Other tensio-active agent for example can use multiple fatty acid ester; Such as but not limited to, glyceryl ester, macrogol ester and sorbitan ester.

Although on certain the level of detail, described the present invention, it being understood that the following example only is used to illustrate the present invention, scope of the present invention is not subjected to the restriction of embodiment.

The composition of hot-melt adhesive of the present invention and character

Hot-melt adhesive of the present invention comprises that mainly (in the hot-melt adhesive final weight) about 40 is to about 100wt%, preferably approximately 60 is to about 85wt%, more preferably about ethylene alpha-olefin interpolymers of 65 to about 80wt%, (in the hot-melt adhesive final weight) 0 are to about 60wt%, preferably approximately 15 is to about 40wt%, one or more tackifier of more preferably about 20 to about 35wt%.

The ethylene alpha-olefin interpolymers component of hot-melt adhesive of the present invention has about 0.880 to about 0.930g/cm ³, preferably approximately 0.890 is to about 0.920g/cm ³, more preferably about 0.8945 to about 0.915g/cm ³, be preferably greater than 0.885g/cm again ³, most preferably greater than 0.895g/cm ³Density.

The ethylene alpha-olefin interpolymers component of hot-melt adhesive of the present invention has about 1,000 to about 9,000, and preferably approximately 1,250 is to about number-average molecular weight of 7,000, more preferably about 1,500 to about 6,000 (Mn measures by GPC).

The ethylene alpha-olefin interpolymers component of hot-melt adhesive of the present invention has about 500 to about 7,000 centipoises, preferably approximately 1,000 to about 6,000 centipoises, more preferably about 1,500 brookfield viscosity (under 300 ℉, measuring) to about 5,000 centipoises.

Hot-melt adhesive of the present invention has about 400 to about 2,000 centipoises, and preferably approximately 500 is to about 1,400 centipoise, more preferably about 750 brookfield viscosity to about 1,200 centipoise (measuring under 350 ℉);

Hot-melt adhesive of the present invention has more than or equal to 110 ℉, is preferably greater than to equal 115 ℉, more preferably greater than the release adhesive fail temperature that equals 120 ℉ (" PAFT ").

Hot-melt adhesive of the present invention has more than or equal to 140 ℉, is preferably greater than to equal 150 ℉, more preferably greater than the shear adhesion fail temperature that equals 170 ℉ (" SAFT ").

Hot-melt adhesive of the present invention shows 100% paper tear (paper tear) between 77 ℉-140 ℉, preferably show 100% paper tear between 35 ℃-140 ℉, most preferably shows 100% paper tear at 140 ℉.

The preparation of embodiment

Unless indicate separately, use the Brookfield VII+ of D. Lab viscometer in disposable aluminium sample chamber, to measure the viscosity of following sample according to follow procedure.Used axle is the SC-31 thermally melting axle that is fit to the viscosity in 10 to 100, the 000 centipoise scopes of measuring.Use cutting blade that sample is cut into enough little small pieces with in the 1 inch wide 5 inches long sample chambers of packing into.Sample is placed the chamber, this chamber is inserted in the Brookfield well heater and with looper head pliers (needle-nose pliers) fix again.There is the groove of applying Brookfield heater base the sample chamber in the bottom, to guarantee that this chamber can not rotated when axle is inserted and rotate.Sample is heated to temperature required, for example 300 ℉ or 350 ℉ append sample until fusing sample approximately to below, top, sample chamber 1 inch again.Viscometer apparatus is reduced and axle is immersed in the sample chamber.Continue to descend and on well heater, aim at (align) until the carriage on the viscometer.Viscometer is opened, and be set as and make the shearing rate of torque reading between 30 to 60%.Per minute is got single reading, got about 15 minutes, and perhaps until its value stabilization, the record last reading.

Unless indicate separately, use standard SAFT method of testing (ASTM D-4498) to carry out the test (be usually used in evaluating and testing fusible test, and be that this industrial technology personnel are known) of shear adhesion fail temperature (" SAFT ").Use ChemInstruments HT-8 stove shearing test machine and 500 gram counterweights to carry out the SAFT test.Test at room temperature begins under (25 ℃/77 ℉), and heats up with 0.5 ℃/minute speed.The result is transformed and Ji Lu Cheng ℉.The SAFT thermometrically temperature during adhesive failure.

Unless otherwise specified, carry out release adhesive fail temperature (" PAFT ") according to ASTM D-D4498 (revising) use 100 gram counterweights at separation mode.PAFT provided when peeling off at 180 ° of angles single coating zone and standard steel plate or with other single tackiness of being with that applies.

Unless indicate separately, carry out fiber tearing % on the fluting board according to the standard industry method of testing, the drops of adhesive that wherein will be heated to 350 ℉ imposes on the paper.1.5 after second, be placed on another paper on the drops of adhesive and be laminated on the basic paper with intended size (11 " * 3 ").With hand two paper are drawn back rapidly, and evaluation and test fiber tearing % (FT).

Unless indicate separately, the fusing point of adhesive formula thing of the present invention uses dsc (" DSC ").Several milligrams of samples are put in the instrument and temperature are risen to 180 ℃ from room temperature with 10 ℃/minute speed.Then sample was placed 3 minutes at 180 ℃ of constant temperature, made temperature reduce to-40 ℃ then with 10 ℃/minute speed.Sample was placed 3 minutes at-40 ℃ of constant temperature.Make temperature rise to 150 ℃ then with 10 ℃/minute speed.According to the second time heating curve record degree of crystallinity and fusing point data.

According to ASTM D792 working sample density.

Dropping point (Mettler dropping point) according to the ASTM3954 working sample.

Unless indicate the following binding property evaluation and test of carrying out formulation of the present invention separately: it is commonly used and available from National Papers in making that formulation is applied to packing case carton, and Minneapolis is on the quantitative kraft paper of the 45# of Minn.

The commercially available material of using in the table 1-evaluation and test

Embodiment 1. uses the preparation of the ethylene alpha-olefin polymer of monometallic ocene catalyst system

The a series of ethylene/alpha-olefin interpolymers of preparation in 1 gallon oil jacket formula autoclave continuous stirred tank reactor (CSTR) (" CSTR ").Mix with the magnetic coupling agitator that has Lightning A-320 impeller.Reactor makes liquid in 475psig (3,275 kPas) current downflow.Processing stream advances from the top from the bottom.Heat passage oil circulates to remove partial reaction heat by the chuck of reactor.At reactor exit is the Micro-Motion that measures flow and solution density ^TMUnder meter.All pipelines on the reactor outlet are all with 50psi (344.7 kPas) steam and by adiabatic.

Supply ISOPAR-E solvent and comonomer with 30psig pressure to reactor.Pass through Micro-Motion ^TMMass flow meter measurement adds the solvent feed of reactor.Bring up to reactor pressure by variable-ratio surge pump control solvent flow rate and with solvent pressure.Pass through Micro-Motion ^TMMass flowmeter measures comonomer and carries out flow control by the Research control valve.Comonomer stream is mixed with solvent streams and itself and solvent one are reinstated in the pump suction reactor.Residual solvent and ethene and the merging of (randomly) hydrogen are sent in the reactor.Just before the Research valve, pass through Micro-Motion ^TMThe mass flow meter measurement ethylene stream is with dominant discharge.Use three Brooks under meter/controllers (1-200sccm and 2-100sccm) hydrogen to be sent into ethylene stream in the outlet of ethene control valve.

Ethene or ethene/hydrogen mixture at room temperature merge with solvent/comonomer stream.Temperature when entering reactor with two heat exchanger control solvent/monomers.Described incoming flow enters the bottom of 1 gallon of CSTR.Three component catalyst systems stream and solvent thereof also enter this reactor in the bottom, but enter by the inlet different with monomer flow.

After having measured solution density, in the reactor product vent pipe, add HP catalyst killer and stop polymerization.Can add other polymeric additive with HP catalyst killer.Reactor stream fluid stream enters in the post-reactor well heater subsequently, and this well heater provides extra energy for the flash distillation of removing solvent.Flash distillation takes place when effluent liquid stream leaves the post-reactor well heater, and reduces to 10 at reactor pressure control valve place pressure from 475psig.

The polymkeric substance of flash distillation enters in the hot-oil jacket formula devolatilizer.About 90% volatile matter in the removal polymkeric substance in this devolatilizer.Volatile matter leaves from the top of devolatilizer.With cooling jacket formula interchanger condensation of residual liquid stream, enter ethylene glycol jacketed type solvent/ethylene separator then.Solvent leaves from container bottom, and ethene is discharged from the top.Use Micro-Motion ^TMThe mass flow meter measurement ethylene stream.Use the measuring result of unreacting ethylene to calculate conversion of ethylene.Isolating polymer and extract out in devolatilizer with toothed gear pump.With product collection in the lining dish and in vacuum drying oven with 140 ℃ of dryings 24 hours.Table 2 has been summarized the polymkeric substance condition, and table 3 has been summarized the character of resulting polymers.

Table 2-ethylene/alpha-olefin interpolymer preparation condition *

Polymkeric substance	Temperature of reactor ℃	Solvent flow rate lb/hr	Ethene flow velocity lb/hr	Octene flow velocity lb/hr	Propylene flow velocity lb/hr	Hydrogen flow rate sccm	C2 transformation efficiency (%)	The B/Ti mol ratio	MMAO/ Ti mol ratio
Polymkeric substance	Temperature of reactor ℃	Solvent flow rate lb/hr	Ethene flow velocity lb/hr	Octene flow velocity lb/hr	Propylene flow velocity lb/hr	Hydrogen flow rate sccm	C2 transformation efficiency (%)	The B/Ti mol ratio	MMAO/ Ti mol ratio	1	150	25.4	2.65	1.37	-	143.8	90.10	1.16	4.99
2	150	25.2	2.65	1.20	-	139.9	90.00	1.23	5.03	1	150	25.4	2.65	1.37	-	143.8	90.10	1.16	4.99
2	150	25.2	2.65	1.20	-	139.9	90.00	1.23	5.03	3	150	25.6	2.65	1.15	-	149.9	90.40	1.21	4.93
4	151	25.0	2.65	1.90	-	167.3	90.22	1.24	5.00	3	150	25.6	2.65	1.15	-	149.9	90.40	1.21	4.93

5	150	25.2	2.65	1.72	-	197.0	89.75	1.21	4.93
5	150	25.2	2.65	1.72	-	197.0	89.75	1.21	4.93	6	151	25.1	2.65	1.85	-	144.2	90.47	1.25	4.97
7	150	25.2	2.65	1.67	-	175.4	90.36	1.20	4.95	6	151	25.1	2.65	1.85	-	144.2	90.47	1.25	4.97
7	150	25.2	2.65	1.67	-	175.4	90.36	1.20	4.95	8	148	25.5	2.65	1.00	-	126.6	89.95	1.15	4.99
9	151	25.2	2.65	1.30	-	111.5	90.09	1.14	4.97	8	148	25.5	2.65	1.00	-	126.6	89.95	1.15	4.99
9	151	25.2	2.65	1.30	-	111.5	90.09	1.14	4.97	10	150	25.1	2.65	1.24	-	108.2	90.42	1.20	9.92
11	148	25.1	2.65	1.35	-	107.9	90.05	1.21	4.99	10	150	25.1	2.65	1.24	-	108.2	90.42	1.20	9.92
11	148	25.1	2.65	1.35	-	107.9	90.05	1.21	4.99	12	148	25.3	2.65	1.15	-	113.9	90.00	1.19	5.01
13	147	25.1	2.65	1.31	-	106.9	90.09	1.24	5.04	12	148	25.3	2.65	1.15	-	113.9	90.00	1.19	5.01
13	147	25.1	2.65	1.31	-	106.9	90.09	1.24	5.04	14	147	25.5	2.65	1.00	-	114.9	90.02	1.15	4.98
15	151	25.2	2.65	1.30	-	83.7	89.88	1.13	4.93	14	147	25.5	2.65	1.00	-	114.9	90.02	1.15	4.98
15	151	25.2	2.65	1.30	-	83.7	89.88	1.13	4.93	16	150.5	25.2	2.65	-	0.60	159.9	90.2	1.22	5.01
17	150.1	25.2	2.65	-	0.75	164.8	89.9	1.20	4.94	16	150.5	25.2	2.65	-	0.60	159.9	90.2	1.22	5.01
17	150.1	25.2	2.65	-	0.75	164.8	89.9	1.20	4.94	18	150.2	25.2	2.65	-	0.45	165.5	90.0	1.18	4.91
19	150.1	25.2	2.65	-	0.90	166.0	89.8	1.20	5.02	18	150.2	25.2	2.65	-	0.45	165.5	90.0	1.18	4.91
19	150.1	25.2	2.65	-	0.90	166.0	89.8	1.20	5.02	20	150.4	25.2	2.65	-	0.70	124.9	90.3	1.26	5.04
21	150.4	25.2	2.65	-	0.52	126.9	89.9	1.21	5.05	20	150.4	25.2	2.65	-	0.70	124.9	90.3	1.26	5.04
21	150.4	25.2	2.65	-	0.52	126.9	89.9	1.21	5.05	22	149.9	25.2	2.62	-	0.70	94.9	90.0	1.22	4.72
23	150.7	25.2	2.65	-	0.52	96.2	90.5	1.20	5.02	22	149.9	25.2	2.62	-	0.70	94.9	90.0	1.22	4.72

^*The catalyzer of the polyreaction that is useful on all is according to United States Patent (USP) 5,556, (the C of 928 embodiment 17 preparations ₅Me ₄SiMe ₂N ^tBu) Ti (η ⁴-1,3-pentadiene), the full content of this patent disclosure is incorporated herein by this reference.The main promotor of all polyreactions all is as United States Patent (USP) #5,919,983, boric acid Armeenium four (pentafluorophenyl group) boric acid [methyl two (the hydrogenated tallow alkyl)] ammonium of preparation among the embodiment 2, the full content of this patent disclosure is incorporated herein by this reference.The less important promotor of all polymeric all is as the modified methyl aluminoxane (MMAO) of MMAO-3A (CAS#146905-79-10) available from Akzo Nobel.

Embodiment 2. contains the preparation of the adhesive formula thing of tackifier

In metal vessel each composition being blended into gross weight is 100 grams.In container, add tackifier resins and be heated 10 minutes with the heating mantles that controlled temperature is used.With the 3-5 minute slow polymkeric substance that adds.Once fusion, just use the metal spatula with moderate speed with each composition manual mixing.After polymkeric substance adds fully, with tackiness agent remix 15 minutes to guarantee evenly.Final tackiness agent temperature is 350-360 ℉ under all situations.In some formulation, use single tackifier, and other formulation is used the tackifier mixture.

The evaluation and test of embodiment 3. adhesive formula things

Use the binding property of aforementioned method of testing evaluation and test according to the adhesive formula thing of embodiment 2 preparations.Table 4-6 has summarized the performance of these adhesive formula things, and compares (table 7) with the performance of some commercial binder.

When evaluation and test fiber tearing in higher temperature range (77 ℉ to 140 ℉), use the most ethylene/alpha-olefin polymers of ethene and 1-octene synthetic to show good performance.In these formulation some are also effective under 35 ℉.

These results show that these polymkeric substance can satisfy the preparation demand in a large amount of adhesive application field with the character of the tackiness agent that combining of tackifier produces.

The result also shows, when these new polymerss and suitable tackifier preparation, has the bond properties that is parity with or superiority over traditional E VA hot-melt adhesive (with wax and tackifier and the preparation of EVA resin).The result also shows when new polymers of the present invention and selected tackifier chemical combination, to have the performance suitable with superfine hot-melt adhesive aspect fiber tearing.

Embodiment 4. heat stability testings

Compare with traditional E VA resin, be well known that the ethenoid resin that metallocenes generates has suitable thermostability.In order to test the thermostability of this new type resin, be 0.9032g/cm with density ³Of the present invention novel POE resin place the convection oven of 350 ℉.Result shown in the table 8 has shown the thermostability of this new polymers.Gardner color is a general approach of measuring the hot-melt adhesive thermal destruction.The generation of color is directly related with thermal destruction; Therefore, Gardner's numerical value is high more, and the color relation that produces in the polymkeric substance is many more.

The thermostability of table 8. new polymers

Time	Observe Gardner color
Time	Observe Gardner color	0 hour	2
48 hours	+ 2, limpid	0 hour	2
48 hours	+ 2, limpid	96 hours	7, limpid

Embodiment 5. uses the bimetal ocene catalyst system to prepare ethylene/alpha-olefin interpolymer

Also be a series of ethylene/alpha-olefin interpolymers of preparation in 1 gallon oil jacket formula autoclave continuous stirred tank reactor (CSTR) (" CSTR ").Mix with the magnetic coupling agitator that has Lightning A-320 impeller.Reactor makes liquid in 475psig (3,275 kPas) current downflow.Process flow is advanced from the top from the bottom.Chuck by reactor carries out heat passage oil circulation to remove partial reaction heat.At reactor exit is the Micro-Motion that measures flow and solution density ^TMUnder meter.All pipelines on the reactor outlet are all with 50psi (344.7 kPas) steam and make its thermal insulation.

Supply ISOPAR-E solvent and comonomer with 30psig pressure to reactor.Pass through Micro-Motion ^TMMass flowmeter is measured the solvent feed that enters reactor.The surge pump of variable velocity is controlled solvent flow rate and solvent pressure is brought up to reactor pressure.Pass through Micro-Motion ^TMMass flowmeter measures comonomer and carries out flow control by the Research control valve.Comonomer stream is mixed with solvent streams and itself and solvent one are reinstated in the pump suction reactor.Residual solvent and ethene and the merging of (randomly) hydrogen are also sent into reactor.Just before the Research valve, pass through Micro-Motion ^TMThe mass flow meter measurement ethylene stream is with dominant discharge.Use three Brooks under meter/controllers (1-200sccm and 2-100sccm) hydrogen to be sent into ethylene stream in the outlet of ethene control valve.

Ethene or ethene/hydrogen mixture at room temperature merge with solvent/comonomer stream.Temperature when entering reactor with two heat exchanger control solvent/monomers.This substance flow enters the bottom of 1 gallon of CSTR.

In an inert atmosphere case, with preparation transistion metal compound solution, provide the final catalyst solution of concentration known and composition thus with the concentrated solution of the appropriate amount of every kind of these two kinds of component and solvent.This solution is transferred in the pressurized vessel under nitrogen, and this pressurized vessel links to each other with the high-pressure metering pump that is used for being transported to polymerization reactor.

In identical inert atmosphere case, the solution of preparation main promotor four (pentafluorophenyl group) boric acid methyl two (hydrogenated tallow alkyl) ammoniums and less important promotor MMAO model 3A in solvent, and as described in to catalyst solution, it is transferred in the independent pressurized vessel.If each volume pump obtains the mol ratio in the polymerization reactor as shown in table 9, determine A1 and the ratio of transition metal (" TM ") and the ratio of boron and TM by the control volume output flow so.Three component catalyst systems and solvent streams thereof also enter reactor in the bottom, but enter by the inlet different with monomer flow.

After having measured solution density, in the reactor product vent pipe, add HP catalyst killer and stop polymerization.Can add other polymeric additive with HP catalyst killer.Reactor stream fluid stream enters in the post-reactor well heater subsequently, and it provides extra energy for the flash distillation of removing solvent.Flash distillation takes place when effluent liquid stream leaves the post-reactor well heater, and reduces to 10 at reactor pressure control valve place pressure from 475psig.

The polymkeric substance of flash distillation enters in the hot-oil jacket formula devolatilizer.About 90% volatile matter in the removal polymkeric substance in this devolatilizer.Volatile matter leaves from the top of devolatilizer.With cooling jacket formula interchanger condensation of residual liquid stream, enter ethylene glycol jacketed type solvent/ethylene separator then.Solvent leaves from container bottom, and ethene is discharged from the top.Use Micro-Motion ^TMThe mass flow meter measurement ethylene stream.Use the measuring result of unreacting ethylene to calculate conversion of ethylene.Isolating polymer and extract out in devolatilizer with toothed gear pump.With product collection in the lining dish and in vacuum drying oven with 140 ℃ of dryings 24 hours.

Can in the interpolymer product, add additive (for example antioxidant, pigment or the like), and with about 1000ppm's

1010 and the IRGAFOS 168 of 2000ppm make all polymer stabilisings.

And IRGAFOS ^TMAll be that Ciba Geigy Corporation makes, and be the trade mark of the said firm.IRGAFOS ^TMThe 168th, phosphites stabilizers,

The 1010th, the polyphenol stablizer that is obstructed (for example, four [methylene radical 3-(3,5-di-tert-butyl-hydroxy phenyl propionic ester)]-methane.Table 9 has been summarized polymerizing condition, and table 10 has been summarized the performance of resulting polymers.

Table 9-ethylene/alpha-olefin interpolymer preparation condition *

Embodiment	Temperature of reactor ℃	Solvent flow rate lb/hr	Ethene flow velocity lb/hr	Octene flow velocity lb/hr	Hydrogen flow rate sccm	C2 transformation efficiency (%)	B ^a/ Tr mol ratio	MMAO ^b/Tr ^cMol ratio	Catalyzer	The mol ratio catalyzer
Embodiment	Temperature of reactor ℃	Solvent flow rate lb/hr	Ethene flow velocity lb/hr	Octene flow velocity lb/hr	Hydrogen flow rate sccm	C2 transformation efficiency (%)	B ^a/ Tr mol ratio	MMAO ^b/Tr ^cMol ratio	Catalyzer	The mol ratio catalyzer	1	150.32	25.20	2.68	1.25	174.48	89.47	1.21	10.07	CATS-1/2	1:1
2	150.50	25.76	2.65	0.86	111.75	89.69	1.47	6.01	CATS-1/2	1:3	1	150.32	25.20	2.68	1.25	174.48	89.47	1.21	10.07	CATS-1/2	1:1
2	150.50	25.76	2.65	0.86	111.75	89.69	1.47	6.01	CATS-1/2	1:3	3	150.38	25.80	2.65	0.76	113.80	90.37	1.51	6.04	CATS-1/2	1:3
4	149.88	25.77	2.65	0.85	150.35	80.15	1.37	5.96	CATS-1/2	1:3	3	150.38	25.80	2.65	0.76	113.80	90.37	1.51	6.04	CATS-1/2	1:3
4	149.88	25.77	2.65	0.85	150.35	80.15	1.37	5.96	CATS-1/2	1:3	5	129.73	20.87	2.65	1.03	97.77	90.46	1.47	5.99	CATS-3/1	1:1
6	130.03	20.81	2.65	1.06	69.90	90.13	1.48	5.83	CATS-3/1	20:1	5	129.73	20.87	2.65	1.03	97.77	90.46	1.47	5.99	CATS-3/1	1:1
6	130.03	20.81	2.65	1.06	69.90	90.13	1.48	5.83	CATS-3/1	20:1	7	119.13	20.78	2.65	1.17	47.98	90.03	1.49	5.93	CATS-3/1	20:1
8	149.65	25.51	2.65	1.00	83.20	90.40	1.06	4.95	CATS-4/1	1:1	7	119.13	20.78	2.65	1.17	47.98	90.03	1.49	5.93	CATS-3/1	20:1
8	149.65	25.51	2.65	1.00	83.20	90.40	1.06	4.95	CATS-4/1	1:1	9	120.28	25.20	2.65	1.60	13.45	90.44	1.08	4.91	CATS-3/1	10:1
10	150.20	25.60	2.65	0.73	121.97	90.35	1.08	4.95	CATS-4/2	1:2	9	120.28	25.20	2.65	1.60	13.45	90.44	1.08	4.91	CATS-3/1	10:1

^aThe main promotor of all polymeric all is as United States Patent (USP) #5,919,983, and boric acid Armeenium four (pentafluorophenyl group) boric acid [methyl two (the hydrogenated tallow alkyl)] ammonium of preparation among the embodiment 2, the full content of this patent disclosure is incorporated herein by this reference.

^bThe less important promotor of all polymeric all is as the modified methylaluminoxane (MMAO) of MMAO-3A (CAS#146905-79-10) available from Akzo Nobel.

^cEmbodiment 1-4,8 and 10 in the his-and-hers watches 11, term Tr refers to total titanium content of hybrid catalyst system.Concerning embodiment 5-7 and 9, term Tr refers to the only Zr content in hybrid catalyst system.

^dCAT 1 is according to United States Patent (USP) 5,556, (the C of 928 embodiment 17 preparations ₅Me ₄SiMe ₂N ¹Bu) Ti (η ⁴-1,3-pentadiene), the full content of this patent disclosure is incorporated herein by this reference.CAT2 is according to United States Patent (USP) 5,150, (dimethyl) (1H-encircles penta [1]-Fei-2-yl) dimethyl (tertiary butyl amido) silane titanium of 297 embodiment 1 and 2 preparations, and the full content of this patent disclosure is incorporated herein by this reference.CAT3 is according to United States Patent (USP) 5,703, (the C of 187 embodiment 1 and 86 preparations ₅Me ₄SiMe ₂N ¹Bu) ZrMe ₂, the full content of this patent disclosure is incorporated herein by this reference.CAT 4 be according to the embodiment 1 of WO 02/092610 and 2 the preparation [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[1,2,3,4,5-η]-3,4-phenylbenzene-2,4-cyclopentadienyl-1-yl] silanaminato (2)-κ N]-dimethyl-titanium, the full content of this patent disclosure is incorporated herein by this reference.

Embodiment 6. uses ethylene/alpha-octene copolymer system of embodiment 5 to contain the adhesive formula thing of tackifier fully

Described in front embodiment 2, each composition ad pond om of fusion hot-melt adhesive composition is 100 grams in metal vessel.In container, add tackifier resins and be heated 10 minutes with the heating mantles that controlled temperature is used.With the 3-5 minute slow polymkeric substance that adds.Once fusion, just use the metal spatula with moderate speed with each composition manual mixing.After polymkeric substance adds fully, with tackiness agent remix 15 minutes to guarantee evenly.Final tackiness agent temperature is 350-360 ℉ under all situations.

The evaluation and test of embodiment 7. adhesive formula things

The performance of the adhesive formula thing of embodiment 6 is summarised in the table 11 and compares with the performance of table 7 a generalized commercial binder.

Claims

1. hot-melt adhesive composition, described composition mainly contains:

A) in the hot-melt adhesive composition final weight, 60 to 85wt% even ethylene/alpha-olefin interpolymer, being characterized as of described even ethylene/alpha-olefin interpolymer has 1,000 to 7,000 number-average molecular weight; With

B) in the hot-melt adhesive composition final weight, one or more tackifier of 15 to 40wt%.

2. hot-melt adhesive composition, described composition mainly contains:

A) in the hot-melt adhesive composition final weight, 60 to 85wt% even ethylene/alpha-olefin interpolymer, described even ethylene/alpha-olefin interpolymer are characterised in that to have 1,000 to 7,000 number-average molecular weight; With

B) in the hot-melt adhesive composition final weight, one or more tackifier of 15 to 40wt%; And wherein, in described binder composition

C) described even ethylene/alpha-olefin interpolymer is further characterized in that to have:

I) 0.890 to 0.920g/cm ³Density;

Ii) 5 to 70 gram/brookfield viscosity 149 ℃ of measurements of (cm. seconds); With

D) described hot-melt adhesive composition is characterised in that and has

I) the brookfield viscosity of 4 to 20 gram/(cm. seconds) 177 ℃ of mensuration;

Ii) more than or equal to 43 ℃ release adhesive fail temperature; With

Iii) more than or equal to 60 ℃ shear adhesion fail temperature.

3. hot-melt adhesive composition according to claim 1, wherein:

A) in the hot-melt adhesive composition final weight, evenly the amount of ethylene/alpha-olefin interpolymer is 65 to 80wt%, and this even ethylene/alpha-olefin interpolymer is characterised in that to have:

I) 0.890 to 0.920g/cm ³Density;

Ii) 1,250 to 7,000 number-average molecular weight; With

Iii) 10 to 60 gram/brookfield viscosity 149 ℃ of mensuration of (cm. seconds);

With

B) in the hot-melt adhesive composition final weight, the amount of described one or more tackifier is 20 to 35wt%; And wherein

C) hot-melt adhesive composition is characterised in that and has:

I) have 5 to the 14 gram/brookfield viscosity 177 ℃ of mensuration of (cm. seconds);

Ii) has release adhesive fail temperature more than or equal to 46 ℃; With

Iii) has shear adhesion fail temperature more than or equal to 66 ℃; With

Iv) under 2 ℃-60 ℃, show 100% paper tear.

4. hot-melt adhesive composition according to claim 1, wherein:

A) described even ethylene/alpha-olefin interpolymer is characterised in that to have:

I) 0.895 to 0.915g/cm ³Density;

Ii) 1,500 to 6,000 number-average molecular weight; With

Iii) 15 to 50 gram/brookfield viscosity 149 ℃ of mensuration of (cm. seconds);

And

B) described hot-melt adhesive composition is characterised in that:

I) have 7.5 to the 12 gram/brookfield viscosity 177 ℃ of mensuration of (cm. seconds);

Ii) has release adhesive fail temperature more than or equal to 49 ℃;

Iii) has shear adhesion fail temperature more than or equal to 77 ℃; With

Iv) in-18 ℃ of-60 ℃ of scopes, show 100% paper tear.

5. hot-melt adhesive according to claim 1, wherein:

A) evenly ethylene/alpha-olefin interpolymer is further characterized in that to have:

I) 0.893 to 0.930g/cm ³Density;

Ii) 1,000 to 6,000 number-average molecular weight; With

And

B) described hot-melt adhesive composition is characterised in that:

I) have 4 to the 14 gram/brookfield viscosity 177 ℃ of mensuration of (cm. seconds);

Ii) has release adhesive fail temperature more than or equal to 32 ℃; With

Iii) has shear adhesion fail temperature more than or equal to 93 ℃; With

Iv) show 100% paper tear at 60 ℃.

6. hot-melt adhesive composition according to claim 5, wherein:

A) evenly ethylene/alpha-olefin interpolymer is characterised in that to have:

I) 0.894 to 0.910g/cm ³Density;

Ii) 1,100 to 5,300 number-average molecular weight; With

Iii) 16 to 32 gram/brookfield viscosity 149 ℃ of mensuration of (cm. seconds);

And

B) described hot-melt adhesive composition is characterised in that:

I) have 7 to the 12 gram/brookfield viscosity 177 ℃ of mensuration of (cm. seconds);

Ii) has release adhesive fail temperature more than or equal to 32 ℃; With

Iii) has shear adhesion fail temperature more than or equal to 93 ℃; With

Iv) show 100% paper tear at 60 ℃.

7. according to claim 2,3,4 or 6 each described hot-melt adhesive compositions, wherein:

A) evenly ethylene/alpha-olefin interpolymer is ethene and one or more C ₃-C ₃₀The interpolymer of alpha-olefin; And

B) described one or more tackifier are selected from aliphatic hydrocarbon resin, hydrogenated hydrocarbon resins or aromatic hydrocarbon resin or aromatic modified C ₅Aliphatic series or aromatic hydrocarbon resin or their mixture;

And

Wherein binder composition can be adhered to cellulosic cellulosics and be selected from the following goods: cellulosic cellulosics, timber, metal, glass, plastics or their mixture.

8. hot-melt adhesive composition according to claim 7, wherein aliphatic hydrocarbon resin is C ₅Aliphatic hydrocarbon resin.

9. according to claim 4 or 5 described hot-melt adhesive compositions, wherein:

A) in even ethylene/alpha-olefin interpolymer, alpha-olefin is selected from C ₃, C ₈, C ₁₀, C ₁₂, C ₁₄, C ₁₆, C ₁₈, C _20-30Or their mixture; And

B) described one or more tackifier are characterised in that and have 0 to 25.8 acid number.

10. hot-melt adhesive composition according to claim 9, wherein C ₃Be propylene, C ₈Be 1-octene, C ₁₀Be 1-decene, C ₁₂Be 1-laurylene, C ₁₄Be 1-tetradecylene, C ₁₆Be 1-hexadecylene and C ₁₈Be the 1-octadecylene.

11. according to claim 7 or 9 described hot-melt adhesive compositions, described composition further comprises one or more compounds, described compound is selected from stablizer, softening agent, weighting agent, antioxidant, sanitas, synergist, dyestuff or pigment.

12. hot-melt adhesive composition according to claim 9, wherein alpha-olefin is selected from 1-octene or propylene.

13. according to claim 9 or 12 described hot-melt adhesive compositions, wherein multipolymer has 2.1 to 16 molecular weight distribution.

14. according to claim 9,12 or 13 described hot-melt adhesive compositions, wherein, in the hot-melt adhesive composition final weight, the amount of tackifier is 15 to 35wt%.

15. a cellulosics that uses hot-melt adhesive composition to form, described binder composition mainly contains:

16. cellulosics according to claim 15, wherein in hot-melt adhesive composition:

A) in the hot-melt adhesive composition final weight, evenly the amount of ethylene/alpha-olefin interpolymer is 60 to 85wt%, and this even ethylene/alpha-olefin interpolymer is characterised in that to have:

I) 0.880 to 0.930g/cm ³Density;

Iii) 5 to 70 gram/brookfield viscosity 149 ℃ of mensuration of (cm. seconds),

And

B) hot-melt adhesive composition is characterised in that and has:

Ii) more than or equal to 43 ℃ release adhesive fail temperature; With

Iii) more than or equal to 60 ℃ shear adhesion fail temperature.

17. cellulosics according to claim 15, wherein in hot-melt adhesive composition:

A) account for the hot-melt adhesive composition final weight, evenly the amount of ethylene/alpha-olefin interpolymer is 65 to 80wt%, and this even ethylene/alpha-olefin interpolymer is characterised in that to have:

I) 0.890 to 0.920g/cm ³Density;

Ii) 1,250 to 7,000 number-average molecular weight; With

With

C) hot-melt adhesive composition is characterised in that and has:

Ii) has release adhesive fail temperature more than or equal to 46 ℃; With

Iii) has shear adhesion fail temperature more than or equal to 66 ℃; With

Iv) show 100% paper tear at 60 ℃.

18. cellulosics according to claim 15, wherein in hot-melt adhesive composition:

A) evenly ethylene/alpha-olefin interpolymer is characterised in that to have:

I) 0.893 to 0.930g/cm ³Density;

Ii) 1,000 to 6,000 number-average molecular weight; With

And

B) described hot-melt adhesive composition is characterised in that:

Ii) has release adhesive fail temperature more than or equal to 32 ℃; With

Iii) has shear adhesion fail temperature more than or equal to 93 ℃; With

Iv) show 100% paper tear at 49 ℃.

19. cellulosics according to claim 18, wherein in hot-melt adhesive composition:

A) evenly ethylene/alpha-olefin interpolymer is characterised in that to have:

I) 0.894 to 0.910g/cm ³Density;

Ii) 1,100 to 5,300 number-average molecular weight; With

And

B) described hot-melt adhesive composition is characterised in that:

Ii) has release adhesive fail temperature more than or equal to 32 ℃; With

Iii) has shear adhesion fail temperature more than or equal to 93 ℃; With

Iv) show 100% paper tear at 60 ℃.

20. according to claim 18 or 19 described cellulosicss, wherein in hot-melt adhesive composition:

B) described one or more tackifier are selected from aliphatic hydrocarbon resin, hydrogenated hydrocarbon resins or aromatic hydrocarbon resin or aromatic modified C ₅Aliphatic series or aromatic hydrocarbon resin or their mixture.

21. hot-melt adhesive composition according to claim 20, wherein aliphatic hydrocarbon resin is C ₅Aliphatic hydrocarbon resin.

22. cellulosics according to claim 20, wherein in hot-melt adhesive composition:

23. cellulosics according to claim 22, wherein C ₃Be propylene, C ₈Be 1-octene, C ₁₀Be 1-decene, C ₁₂Be 1-laurylene, C ₁₄Be 1-tetradecylene, C ₁₆Be 1-hexadecylene, C ₁₈Be the 1-octadecylene.

24. cellulosics according to claim 22, wherein cellulosics is selected from Corrugated Box, kraft paper, liner board or paper.

25. a method of making polymer composition, this method comprises the following steps:

Mix:

In the polymer composition final weight, 60 to 85wt% even ethylene/alpha-olefin interpolymer, described even ethylene/alpha-olefin interpolymer is characterised in that to have:

I) 0.880 to 0.930g/cm ³Density;

Ii) 1,000 to 7,000 number-average molecular weight; With

Iii) 5 to 70 gram/(cm. seconds) the brookfield viscosity of 149 ℃ of mensuration and

In the polymer composition final weight, mix 15 to 40wt% tackifier; And wherein

Described polymer composition is characterised in that to have:

Ii) more than or equal to 43 ℃ release adhesive fail temperature; With

Iii) more than or equal to 60 ℃ shear adhesion fail temperature.

26. the method for manufacturing polymer composition according to claim 25, wherein:

A) evenly ethylene/alpha-olefin interpolymer is characterised in that to have:

I) 0.893 to 0.930g/cm ³Density;

Ii) 1,000 to 6,000 number-average molecular weight; With

And

B) described polymer composition is characterised in that:

Ii) has release adhesive fail temperature more than or equal to 32 ℃; With

Iii) has shear adhesion fail temperature more than or equal to 93 ℃; With

Iv) show 100% paper tear at 60 ℃.