WO1997019130A1

WO1997019130A1 - Process for the preparation of a thermoplastic elastomer

Info

Publication number: WO1997019130A1
Application number: PCT/NL1996/000433
Authority: WO
Inventors: Albertus Otto Dozeman; Pieter Gijsman; Herman Augustinus Johannes Schepers; Wilhelmus Antonius Maria Debets
Original assignee: Dsm N.V.
Priority date: 1995-11-17
Filing date: 1996-11-06
Publication date: 1997-05-29
Also published as: MX9803933A; AU7343696A; BR9611601A; CZ153398A3; CN1207750A; EP0861289A1; ZA969585B; JP2000500523A; CA2237989A1

Abstract

The invention relates to a process for the preparation of a thermoplastic elastomer comprising preparing a blend of a rubber and a thermoplastic resin, in which the rubber is at least partially vulcanized by using a phenolic curative. The invention is that, to overcome problems with surface quality, an effective amount of a Lewis base is added after the desired degree of vulcanization of the rubber is obtained. The invention also relates to a process for the preparation of a UV-stable thermoplastic elastomer.

Description

PROCESS FOR THE PREPARATION OF A THERMOPLASTIC ELASTOMER

The invention relates to a process for the preparation of a thermoplastic elastomer comprising preparing a blend of a rubber and a thermoplastic resin in which the rubber is at least partially vulcanized by using a phenolic curative.

Such a process is Known trom USP 4,311,628, where a vulcanized (or cured) thermoplastic elastomer (or thermoplastic vulcanizate, TPV) is made from a polyolefin resin and an EPDM rubber. The phenolic cura¬ tive, used to prepare such a TPV, generally comprises a phenolic resin, sometimes in the presence of a cure activator; the activator generally includes metal salts and halogen donors. A defect of the known process is that pro¬ ducts made from the so-obtained thermoplastic vulcani- zates often show surface cracking within a short period of time. The products often have an undesired surface roughness. Another problem is the low efficiency of hindered amine light stabilizer-compounds (the socalled HALS-compounds) , added as UV-stabilizer , compared to their efficiency in thermoplastic resin compounds.

Surprisingly it has been found that the above mentioned problems can be significantly reduced or even completely solved, which results in a thermoplastic elastomer with improved physical, especially surface properties.

The invention is characterized in that an effective amount of a Lewis base is added after the desired degree of vulcanization of the rubber is obtai¬ ned.

According to the Lewis definition, a base is a substance that can furnish an electron pair to form a covalent bond. Thus a base is an electron-pair donor. This is the most fundamental of the base concepts, and the most general; it includes all the other concepts, like the Lowry-Brønsted definition, according to which an base is a substance that takes up a proton. The rubber to be used in the process for the preparation of the thermoplastic elastomer according to the present invention may be any natural or synthetic rubber which can be cured with a phenolic curative. This is especially the case for ethylene α-olefin diene terpolymer (EADM) and for butylrubber. The EADM-rubber contains as the second monomer an α-olefin, which can be propylene, butene-1, pentene-1, hexene-1, octene-1 or the like or a branched isomer thereof like 4-methyl- pentene-1, and further styrene, α-methylstyrene and the like. Also mixtures of α-ole- fins are applicable. Preference is given to propylene and/or butene-1 as the α-olefin. Greater preference is given to propylene; the resulting terpolymer is an ethylene/propylene/diene terpolymer (EPDM) . The third monomer in such an EADM or EPDM can be any conventionally applied monomer in such rubber, like hexadiene-1 , 4 , dicyclopentadiene or ethylidene norbornene. Preference is given to ethylidene norborne¬ ne as third monomer. The butylrubber, when used as the essential rubber element of the thermoplastic elastomer of the present invention, can be an amorphous copolymer of isobutylene and isoprene or an amorphous terpolymer of isobutylene, isoprene and a divinyl aromatic monomer. The term "butylrubber" also comprises the halogenated form of the above mentioned co- and terpolymer. Thermo¬ plastic elastomers based on butylrubber are disclosed in e.g. USP 4,130,534 and EP-A-376 ,227.

The thermoplastic resin to be used in the process for the preparation of the thermoplastic elas¬ tomer according to the present invention 'ha be any polymer which behaves like a ther oplast in the tempe- rature range between 100 and 350°C; care should be taken that the processing temperature (i.e. the tempe¬ rature at which the thermoplastic elastomer is prepared or used) is sufficiently lower than the decomposition temperature of the resin. Examples of such resins are thermoplastic resins like polyesters, nylons, polycar¬ bonates, styrene/acrylonitril copolymers as well as the preferred thermoplastic polyolefin resins. In the lat¬ ter case, preference is given to polyethylene and polv- propylene, either as homopolymer or as copolymer.

The thermoplastic elastomer resulting from the process generally comprises 20-500 parts of rubber per 100 parts of thermoplastic resin, more preferably between 30-400 parts and most preferred between 50 and 300 parts.

The rubber in the thermoplastic elastomer is at least partially cured with the phenolic curative. Any phenolic curing system which cures the rubber is suitable in the invention. Preference can be given to the phenolic curing systems mentioned in the above cited USP '628 (indicating both the phenolic curing resin and the cure activator).

In the present process for the preparation of the thermoplastic elastomer the rubber is at least partially vulcanized. One method for determining the degree of vulcanization is by measuring the amount of rubber, extractable from the prepared product by using boiling xylene as the extractant. Such a method can be found in the earlier mentioned USP '628. According to such a method, the rubber in the thermoplastic elastomer prepared in the process of the invention is vulcanized to the extent that not more than 50%, preferably not more than 15% and even more preferred not more than 5% of the rubber is extractable in boiling xylene.

In the process of the present invention an effective amount of a Lewis base is added at a moment where the desired degree of vulcanization of the rubber is obtained. As a rule, an amount of 0.1-10 parts of the Lewis base, per 100 parts of rubber and thermoplas¬ tic resin, is sufficient and effective to obtain the benificial effects of the present invention. More pre¬ ferably, an amount of 0.25-5 parts is used.

Any ingredient which behaves like a Lewis base according to the given definition is suitable for use in the present invention. Components which can be used as the Lewis base are, for example, :

- metal oxides, like magnesium oxide or zinc oxide,

- hydrotalcites,

- amine-functional dendrimers,

- polyethers, - epoxides,

- metal hydroxides (like Mg(OH)₂),

- metal carbonates (like CaC0₃).

Preference is given to the use of a compound selected from the group of hydrotalcites. The hydrotalcite material may be a natural mineral or a synthetic hydrotalcite-1ike material; it may be used in dried (calcined or anhydrous) or parti¬ ally dried form. When it contains a surface active agent, the latter is preferably anionic. The hydrotalcite materials useful in the method of the invention are generally defined as "mag¬ nesium-aluminium-hydroxide carbonate hydrates", but they need not contain carbonates for the purposes of the present invention. An example of a synthetic hydrotalcite is a material having the formula Mg₆Al₂(OH)₁₆C0₃.4H₂0. A synthetic hydrotalcite-like compound available from Kyowa Chemical Company Ltd. under the tradename DHT-4A has the formula Mg₄._sAl₂(0H)₁₃C0₃.3.5 H₂0. A form contai- ning less water of hydration (i.e. less than 3.5 moles of water of hydration per mole of compound) is designa¬ ted DHT-4AA. One group of suitable carbonate free hydro- talcite-like materials has the formula:

Mg-__xAl_x(OH)₂A^b-_χ/b.dH₂0

in which x is greater than 0 and less than or equal to 0.5, d is zero or a positive number, b is a positive integer, and A^b" is an anion having the valency of b. Such materials are described in USP 4,284,762 and 4,347,353.

Synthetic hydrotalcites are also described in detail in Clays and Clay Minerals, 28 , No. 1 at page 50-56 (1980). Another type of (carbonate-free) hydrotalcite material suitable for use in the process of the inven¬ tion has the formula:

Mg₁__xAl_x(OH)_2+x .aH₂0,

in which 0 < x <_. 0.5 and 0 <_. a < 2. This type of mate¬ rial is described in USP 4,379,882.

The addition of an effective amount of a Lewis base is also beneficial for preparing thermo- plastic elastomers to which UV-stabilizers, like in the form of HALS-compounds , are added. The efficiency of such HALS-compounds is significantly improved when using the process of the present invention.

The addition of HALS-compounds alone (i.e. without using the addition of the Lewis base) does only bring a temporary UV-stability of the thermoplastic elastomer. After a relative short period of time the UV-stability deteriorates. This problem is overcome by adding, according to the process of the present inven- tion, to the blend, after the desired degree of vulca¬ nization is obtained, an effective amount of both the Lewis base and the HALS-compound. The skilled man is aware of the commercial existence of different types of HALS-compounds, which he can select for its purpose. As examples of such compounds can be mentioned: Tinuvin®123; 144; 622; 765; 770 and 780, Hals®57; 62; 63; 68; Dastib®845, Uvinul®- 4050, Chimasorb®-944 and HMBTAD®, all compounds being based on the effectiveness of the presence of one or more piperidinyl-groups.

A criterium for the HALS-compound iε that it on one hand is not too volatile under processing condi¬ tions (i.e. at temperatures between 100 and 300°C) as a result of which the compound could evaporate from the thermoplastic elastomer, and on the other hand be suf¬ ficient mobile to be able to migrate through the pro- duct. This is preferably achieved when the HALS com¬ pound has a molecular weight between 250 and 5000, more preferably between 300 and 1000.

The HALS-compound used in preparing the ther¬ moplastic elastomer is generally used in an amount not exceeding 7.5 wt.% per 100 wt.% of the thermoplastic elastomer? more preference is given to an amount not exceeding 5 wt.%; even more preferred is an amount of 0.1-2.5 wt.%.

It is preferred that in the process for pre- paring the at least partially cured thermoplastic elas¬ tomer, a blend comprising uncured rubber and thermo¬ plastic resin is first treated with the phenolic cura¬ tive and thereafter the Lewis base (and if used the HALS compound; preferably in the sequence: first the Lewis base and then the HALS-compound) is added. Then optimal results are obtained.

The process for preparing the thermoplastic elastomer can be any process by which a blend of an at least partially cured rubber and a thermoplastic resin can be obtained. Preference is given to a process in which the blend is made by dynamic curing (i.e. the process of mixing and curing of the rubber and the thermoplastic resin are taking place in the same pro¬ cess step). It is to the skilled man to avoid severe premature vulcanization (curing) while the mixing pro¬ cess is not completed. Reference can be given to the above mentioned USP '628 and USP '534. Equipment quali¬ fied to be used in a process according to the invention can be any mixing apparatus for blending polymers. The process can be executed in batch equipment (like Banbu- ry mixers); preference is given to the use of continu- ous operating equipment, like a twinscrew extruder.

Care should be taken that all ingredients become well- mixed.

It is also possible to prepare the thermo¬ plastic elastomer of the present invention by first preparing a blend of already, at least partially, vul¬ canized rubber with the thermoplastic resin and adding to said blend an effective amount of the Lewis base, and where appropriate, the HALS-compound. Care should be taken that the particle size of the so-used rubber is sufficiently small (in the order of 1-50 μm ) in order to obtain adequate properties.

Next to the above mentioned ingredients the thermoplastic elastomer can contain other additives and fillers commonly used in these types of products, like carbon black, pigments, flame retardants, processing aids, extender oils etc.

In the thermoplastic elastomer of the inven¬ tion preferably also an UV-absorber is present. Such an absorber is known per se; reference can be made to J. Pospisil and P.P. Klemchuck in: "Oxidation inhibition in Organic Materials", vol. I, pag. 23 ff (1990). Exam¬ ples of UV absorbers are cyanoacrylates, phenylsalicy- lates, oxanilides, (di )hydroxybenzophenones and hy- droxyphenylbenzotriazoles. The products obtainable by a process accor¬ ding to the present invention are useful for making a variety of articles like hoses or mouldings. These articles can be made by extrusion, injection or com¬ pression moulding techniques. They are especially use¬ ful in those type of applications where surface proper¬ ties and UV-stability play a major role. The invention will be elucidated by the fol¬ lowing examples and comparative experiments. They are not intended to form in any way a restriction of the invention.

Examples

Comparitive Experiment A

A thermoplastic vulcanizate was prepared in a twinscrew extruder by dynamic vulcanization of a blend of 38 parts of polyp opylene and 124 parts of an EPDM- rubber (comprising 50 wt% of extender oil), under the influence of a curing system comprising (per 100 parts of EPDM) 5 parts of a phenolic curing resin (Schenact- ady SP1045) and 2.5 parts of SnCl₂.2H₂0 as activator. This resulted in a thermoplastic vulcanizate with a rubber extractable content in boiling xylene of 2.5%. To 100 parts of this TPV was added 1 part of Tinuvin 770 as UV-stabilizer ; the so-obtained product was te¬ sted for UV-stability in a Wheather-O-Meter (W.O.M. Ci- 64A (Xenon lamp, intensity 0.35 W/m² at 350 nm, boro- bσro silicate filters, black panel temperature: 63°C, dry-wet cycle, 102/18 min. and 55% rel. humidity)). After a wheathering time of only 1000 hours the first surface cracks were observed.

Example I

To the same TPV as in Comparative Experiment A was added 2 parts of DHT-4A, followed by 1 part of Tinuvin 770 (all per 100 parts of TPV). The first sur- face cracks were observed after a wheathering time of more than 4000 hours. Comparative Experiment B

The process of Comparative Experiment A was used to prepare a TPV comprising 48 parts of polypropy¬ lene and 104 parts of an EPDM-rubber (comprising 50 wt% of extender oil). The amount of curing system used was (per 100 parts of EPDM) 2.5 parts of phenolic curing resin (Schenactady SP1045) and 2.5 parts of SnCl₂.2H₂0 as activator. This resulted in a TPV having a rubber extractable content of 8.5%. To 100 parts of this TPV were added 1.5 parts of an UV- absorber (Tinuvin 328) plus 1.5 parts of the UV-stabi- lizer Tinuvin 770. After 500 hours of wheathering time in QUV the retention of mechanical properties was de¬ termined: the retention in tensile strength (σ_b) was 91.3%; the retention in elongation at break (ε_b) was 84.2%.

Example II

To 100 parts of the TPV of Comparitive Expe- riment B were added 2 parts of DHT-4A, after which 1.5 parts of Tinuvin 238 and 1.5 parts of Tinuvin 770 were added. The retention results of the mechanical proper¬ ties (tested under the same conditions as in Comparati¬ ve Experiment B) were:

= 110.9% = 102.1%

Comparative Experiment C

Comparative Experiment B was repeated, but with 0.75 parts of Tinuvin 328 and 0.75 parts of Tinu¬ vin 770. The retention results were:

σ_b = 90.7% 52.9

Example III

Example II was repeated, but with 0.75 parts of Tinuvin 328 and 0.75 parts of Tinuvin 770. The re- tention results were:

σ_b = 102.8% ; ε_b = 94.2%

Comparative Experiment D

A TPV having the composition as described in Comparative Experiment A was prepared through a dynamic vulcanisation in a Banbury mixer, whereafter the pro¬ duct was fed to an extruder for pellatizing. Thereafter the granulate was extruded into a strip and this strip was judged on surface roughness; by hand, with the use of a microscope with a 200-fold magnification and using a Surftest (based on DIN 4768). The result was: a) a rough touch, as felt with the tip of the finger; b) large surface roughness, seen through the micro¬ scope; c) the average roughness R_a, according to the surf- test and based on the formula:

L 1 r

R_a = ~ J f (x)dx, o with L = measuring length, f(x) = surface roughness curve, measured 5 times (with L being 2.5 cm), had a value of 5.1 μm.

Example IV An analogous process as described in Compara¬ tive Experiment D was performed but at the end of the mixing process in the Banbury mixer, an amount of 0.5 parts of DTA-4A (per 100 parts of TPV) was added to the contents of the Banbury mixer. Thereafter the product was fed to an extruder for pelletizing after which the granulate was extruded into a strip which was judged on surface roughness. The result was: a) a smooth touch, as felt with the tip of the fin- ger ; b) a microscopic much less rough surface; c) in the Surftest an R_a-value of 1.5 μm was determi¬ ned.

Claims

C L A I M S

1. Process for the preparation of a thermoplastic elastomer, comprising preparing a blend of a rub¬ ber and a thermoplastic resin, in which the rubber is at least partially vulcanized by using a phe¬ nolic curative, characte ised in that an effective amount of a Lewis base is added after the desired degree of vulcanization of the rubber is obtained.

2. Process according to claim 1, characterized in that the Lewis base used is a compound selected from the group of hydrotalcites.

3. Process according to any one of claim 1-2, charac- terized in that the Lewis base is used in an amount of 0.25-5 parts, per 100 parts of rubber + thermoplastic resin.

4. Process according to claim 1, characterised in that the rubber used is selected from EADM rubber and butyl rubber.

5. Process according to claim 4, characterised in that the EADM rubber used is a terpolymer of ethy¬ lene, propylene and ethylidene norbornene.

6. Process according to any one of claims 1-5, cha- racterised in that the thermoplastic resin used is a thermoplastic polyolefin resin.

7. Process according to claim 6, characterised in that the thermoplastic resin used is selected from polyethylene and polypropylene.

8. Process according to any one of claims 1-7, cha¬ racterised in that the rubber in the thermoplastic elastomer is vulcanized to the extent that not more than 15% of the vulcanizable rubber is ex¬ tractable in boiling xylene.

9. Process according to claim 8, characterised in that the rubber is vulcanized to the extent, that not more than 5% of the vulcanizable rubber is extractable in boiling xylene.

10. Process according to any one of claims 1-9, cha¬ racterised in that in the preparation of the elas¬ tomer 30-400 parts of rubber per 100 parts of thermoplastic resin are used.

11. Process according to anyone of claims 1-10, cha- racterized in that after the desired degree of vulcanization is obtained also an effective amount of a HALS-compound is added.

12. Process according to claim 11, characterised in that the added HALS-compound has a molecular weight between 250 and 5000.

13. Process according to claim 12, characterised in that the added HALS-compound has a molecular weig¬ ht between 300 and 1000.

14. Process according to any one of claims 11-13, characterised in that the added HALS-compound is used in an amount not exceeding 5 wt.%.

15. Process according to claim 14, characterised in that the added HALS-compound is used in an amount between 0.1 and 2.5 wt.%.