CN1222539A - Use of polyolefine wax in solvent pasty materials - Google Patents

Abstract

The present invention relates to the use of polyolefin waxes synthesized by means of metallocene catalysts for the preparation of solvent-containing pastes. The pastes prepared in this way have a significantly higher paste hardness and an improved heat stability.

Description

The purposes of polyolefin-wax in solvent pasty materials

The present invention relates to be particularly suitable for preparing the polyolefin-wax of solvent-laden wax thickener.

Polyolefin-wax, particularly polyethylene wax are widely used as preparing and for example are used for the recipe ingredient that contains solvent pasty materials of floor care, automobile and footwear and (consult: the industrial chemistry encyclopaedia of Ullmann, the 5th edition, A28 volume, the 108th, 153,156 pages, Wei En Haimu, 1996) (cf:Ullmann ' sEncyclopedia of Industrial Chemistry, 5th Edition, Vol.A28, Pages108,153,156, Weinheim, 1996).Form the wax thickener by the wax solution cooling that makes the heat in the organic solvent.The form of sticking with paste makes wax use and is easy to: with thickener machinery be coated be layered on the surface to be processed after, solvent evaporation fallen and stayed one deck protective or in other words be active cere.

Contain in the prescription of thickener of polyolefin-wax and use other wax for example massive paraffin, little wax and purified carnauba wax or partial hydrolysis and/or unhydrolysed montanin wax and other auxiliary agent that is used to finely tune such as metallic stearate usually.Hydro carbons for example contains aromatic hydrocarbons or aromatic free gasoline or turps usually as solvent.

The performance of the quality-determining of this thickener is except surface property (gloss) and thermostability, (this point is consulted: soap-oil-fat-wax (Seifen-Ole-Fette-Wachse) to also have its denseness, No.20/1957, Page595) latter's the parameter of measuring is exactly so-called thickener hardness usually, can measure the stability of sticking with paste body by it.Here quality criteria be pure wax (" solvent uptake ") with reality in form the thickener hardness of sticking with paste the mixture (becoming the paste capacity) that slower wax set of dispense makes with other.Thickener hardness also is that conclusive importance is arranged to the dependency of temperature and period of storage to evaluation.

Used polyolefin-wax component polyethylene wax importantly in the paste formula particularly contains those of side chain branched chain.Such wax can get by the height polymeric vinyon thermal destruction preparation of branching or by the ethene direct polymerization.Possible polymerization process has for example high-pressure process, therein ethylene changes into the wax of branching by free radical under High Temperature High Pressure, also have low pressure or Ziegler (ziegler) method in addition, therein ethylene passes through the organo-metallic catalyst polymerization under relatively low pressure and temperature.If use low-pressure process, usually by for example propylene or 1-butylene copolymerization are introduced Polyethylene Chain with branched chain with the long-chain olefin monomer of ethene and major part or small portion.

A variant as low-pressure process discloses a kind of method recently, and wherein Metallocenic compound is as organo-metallic catalyst.These compounds contain titanium, zirconium or hafnium atom as spike and usually for example organoaluminum or the preferred aluminium alkoxide compound of boron compound are used in combination with promotor.If desired, under the condition that hydrogen exists as molecular weight regulator, carry out polymerization.The metallocenes method can be distinguished by the following fact: compare with old Ziegler technology, the wax that the metallocenes method obtains has the polymerization of narrower molecular weight distribution, more uniform comonomer, lower fusing point and higher catalyst production.

For example in EP-A-571882, recorded and narrated the corresponding polymerization process for preparing polyolefin-wax with metalloscene catalyst catalysis.

Find now to be particularly suitable for paste formula by the polyolefin-wax of metalloscene catalyst preparation.Compare with the polyethylene wax of routine by the thickener hardness of such wax preparation and to be significantly increased.This not only be applicable to solvent uptake but also be applicable to as with the mixture of other wax become to stick with paste capacity.

The thermostability of this thickener also is improved.Because also not about the molecular structure of polyethylene wax and they data to the relation of the suitability that becomes paste, this result's discovery is wonderful especially up to now.

Therefore the present invention relates to preparation improved the purposes that contains solvent pasty materials of quality by metalloscene catalyst synthetic polyolefin-wax.

Possible polyolefin-wax has the homopolymer of ethene or the multipolymer of ethene and one or more 1-alkene.What the 1-alkene that uses had linear or branching has 3-18 carbon atom, the preferably alkene of 3-6 carbon atom.The example of these alkene has propylene, 1-butylene, 1-hexene, 1-octene or 1-octadecylene and vinylbenzene.The multipolymer of optimal ethylene and propylene or 1-butylene.Multipolymer contains 70-99.9, the ethene of preferred 80-99% weight.

The dropping point that particularly suitable polyolefin-wax has is 90-130 ℃, and preferred 100-120 ℃, the melt viscosity in the time of 140 ℃ is 10-10,000mpaS, and preferred 50-5000mPaS, density is 0.89-0.96cm in the time of 20 ℃ ³/ g, preferred 0.91-0.94cm ³/ g.

The metalloscene catalyst of preparation polyolefin-wax is that chirality or achiral general formula are M ₁The transistion metal compound of Lx.Transistion metal compound M ₁Lx contains at least one central metal atom M ₁, towering ligand L of bonding, for example cyclopentadienyl ligand at least on it.For example halogen, alkyl, alkoxyl group or aryl also can be bonded in central metal atom M to substituting group in addition ₁On.M ₁Be preferably the element of III in the periodic table of elements, IV, V or VI main group, for example Ti, Zr or Hf.The cyclopentadienyl ligand can be regarded as the cyclopentadienyl that refers to unsubstituted cyclopentadienyl and replacement, as methyl cyclopentadienyl, indenyl, 2-methyl indenyl, 2-methyl benzo indenyl, 2-methyl-4-phenyl indenyl, tetrahydro indenyl or octahydrofluorenyl.Towering ligand can be bridge joint or non-bridge joint, wherein may be single bridge or many bridges, also can connect by loop systems.The term metallocenes also comprises having a more than segmental compound of metallocenes, promptly so-called multinuclear metallocena.These compounds can have any needed replacement form and bridge joint variant.The luxuriant fragment of the single metal of this multinuclear metallocena can be identical or different mutually.The example of this multinuclear metallocena for example is described among the EP-A-632063.

Provided especially among the EP-A-571882 metallocenes general structure and with the example of the activation of promotor.

The following example has proved the present invention, but is not limited to these embodiment.

According to the melt viscosity of DGF-M-III 8 (57) with the following wax of rotary viscosity design determining, press DGF-M III 3 (75) and measure dropping point (German fatty scientific institution standard) (Standards of theGerman Association of Fat Science), measure density according to DIN53479.(Seifen-Ole-Fette-Wachse No.20/1957, the method described in 595 pages is measured thickener hardness with soap-oil-fat-wax.

Embodiment 1:

Following polyethylene wax is used for the test of paste formula.

Table 1

	Preparation method/catalyzer	Melt viscosity/140 ℃ mPaS	Dropping point ℃	Density g/cm 3
					Wax sample 1	Low-pressure polymerization/metallocenes	????680	????107	????0.930
Wax sample 2	Low-pressure polymerization/metallocenes	????610	????109	????0.935
					Wax sample 3	Low-pressure polymerization/metallocenes	????540	????111	????0.939
Wax sample 4	Low-pressure polymerization/metallocenes	????660	????109	????0.932
					Wax sample 5	Low-pressure polymerization/metallocenes	????520	????110	????0.932
Wax sample 6	Low-pressure polymerization/metallocenes	????610	????108	????0.935
					Control sample 1	The Ziegler low-pressure polymerization	????600	????119	????0.930
Control sample 2	High pressure polymerisation	????380	????106	????0.925
					Control sample 3	High pressure polymerisation	????650	????107	????0.926
Control sample 4	High pressure polymerisation	????350	????105	????0.930

Prepare sample 1-6 by metalloscene catalyst by ethylene/propylene copolymer according to the operation steps described in the EP-A-571882.

Embodiment 1,2; The comparative example 1,2: solvent uptake

With 20 parts of tests with the wax fusion and make its temperature reach about 130 ℃.80 parts of tests that are heated to 100 ℃ are poured in the wax melt with gasoline (boiling spread: 140-180 ℃), stir simultaneously.Under continuously stirring, make wax solution be cooled to the test with 2 ℃ (measuring with rotating thermometer) more than the solidification point of wax according to DIN51556 and with mixture pour into one in refrigerator bottom in 16 ℃ of refrigerative tin cans.With mixture cooling 20 minutes, measure thickener hardness after 24 hours 23 ℃ of storages

Table 2

	Embodiment 1	Embodiment 2	The comparative example 1	The comparative example 2
					Test wax	Wax sample 1 (metallocenes wax)	Wax sample 2 (metallocenes wax)	Control sample 1 (Ziegler wax)	Control sample 2 (high pressure wax)
Thickener hardness (g/cm 2) measure storage back mensuration (storage is 1 day under 40 ℃) at 20 ℃	2890 1660	1750 1040	1240 510	770 350

Embodiment has shown that metallocenes wax is better than the product that is made by low pressure or high pressure polymerisation usually.This both had been applicable to that the thickener hardness of measuring under the normal temperature also was applicable to the hardness that records after the storage under the high temperature.

Embodiment 3,4, to this embodiment 3,4: the test of thickener performance in the actual prescription

Table 3 prescription (data are % weight)

Component	% weight
		Hoechst Wax X55 (based on the ester type waxes of the partial hydrolysis of montanin wax)	????8.5
Hoechst Wax KSL (based on the ester type waxes of montanin wax)	????1.5
		Hoechst Wax RT (based on the ester type waxes of montanin wax)	????1.0
Massive paraffin 53/54	????20.0
		Test wax	????2.0
Calcium stearate	????3.0
		Test gasoline	????64.0
	????100.0

It is described that the program of preparation thickener is similar to embodiment 1 and 2.

Table 4 result

	Embodiment 3	Embodiment 4	The comparative example 3	The comparative example 4
					Test wax	Wax sample 1 (metallocenes wax)	Wax sample 2 (metallocenes wax)	Control sample 1 (Ziegler wax)	Control sample 3 (high pressure wax)
The surface	Specular gloss	The glossiness height	The glossiness height	The glossiness height
					Thickener hardness (g/cm 2) measure storage back mensuration (storage is 1 day under 40 ℃) at 20 ℃	????2490 ????320	????2070 ????270	????1770 ????200	????1850 ????220

Embodiment 5,6, and the comparative example 5: the test of thickener characteristic in the shoe cream prescription of rigid prescription

Table 5 prescription (data are % weight)

Component	% weight
		Hoechst Wax O (based on the ester type waxes of the partial hydrolysis of montanin wax)	????9.0
Hoechst Wax E (based on the ester type waxes of montanin wax)	????3.0
		Hoechst Wax LP (based on the sour wax of montanin wax)	????1.8
The little wax of plastics (ceresine)	????1.8
		Massive paraffin 60/62	????9.0
Test wax	????1.8
		Calcium stearate	????1.5
Test gasoline	????72.1
			????100.0

It is described that the preparation procedure of this thickener is similar to enforcement 1 and 2.

Table 6 result

	Embodiment 5	Embodiment 6	The comparative example 5
				Test wax	Wax sample 3 (metallocenes wax)	Wax sample 4 (metallocenes wax)	Control sample 1 (Ziegler wax)
Thickener hardness (g/m 2) measure storage back mensuration down at 20 ℃: 2 hours/30 ℃ 2 hours/40 ℃	2090 790 300	2335 997 385	1308 509 183

Embodiment 7-10, the comparative example 6,7: the test of thickener characteristic in the cheap floor wax prescription

Table 7 prescription (data are % weight)

Component	% weight
		Hoechst Wax OP (based on the ester type waxes of the partial hydrolysis of montanin wax)	????1.5
Test wax	????3.5
		Hydrogenated castor oil	????1.0
Paraffin 60/62	????19.0
		The test oil	????75.0
	????100.0

It is described that the paste preparation program is similar to embodiment 1 and 2.

Table 8 result

	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	The comparative example 6	The comparative example 7
							Test wax	Wax sample 3 (metallocenes wax)	Wax sample 4 (metallocenes wax)	Wax sample 5 (metallocenes wax)	Wax sample 6 (metallocenes wax)	Control sample 1 (Ziegler wax)	Contrast test portion 4 (high pressure wax)
Thickener hardness (g/cm 2) measure 2 hours/30 ℃ 2 hours/40 ℃ of storage back mensuration down at 20 ℃	????3090 ????1236 ????300	????2770 ????1320 ????188	????2105 ????932 ????154	????1753 ????740 ????250	????1466 ????570 ???＜120	????1534 ????805 ???＜120

Claims (8)

1. contain purposes in the solvent pasty materials by metalloscene catalyst synthetic polyolefin-wax in preparation.

2. purposes as claimed in claim 1, use therein ethylene copolymer wax contain 0.1-30% weight one or more have the 1-alkene of 3-18 carbon atom chain length.

3. purposes as claimed in claim 2, wherein 1-alkene has 3-6 carbon atom chain length.

4. as the described purposes of claim 1-3, use therein is the propylene of ethene and 0.1-30% weight or the copolymer waxes of 1-butylene.

5. as the described purposes of claim 1-4, wherein the dropping point of polyolefin-wax is 90-130 ℃, is 10-10 140 ℃ of following melt viscosities, 000mpaS.

6. one kind contains by the solvent wax that contains of metalloscene catalyst synthetic polyolefin-wax and sticks with paste.

7. a wax thickener as claimed in claim 6 also contains massive paraffin, little wax or refining carnauba wax or partial hydrolysis or unhydrolysed montanin wax and other auxiliary agent.

8. one kind as claim 6 or 7 described wax thickeners, contain aromatic hydrocarbons or aromatic free gasoline or turps.