A LUBRICANT WITH A POLYACRYLATE BASED ON C13/15 ACRYLATE

Abstract

The present invention relates to a lubricant comprising a polyacrylate which contains a C.sub.13/15 acrylate in polymerized form, where the C.sub.13/15 acrylate comprises at least 70 wt % of linear and branched C.sub.13 and C.sub.15 alkyl (meth)acrylates. It further relates to the polyacrylate, to the C.sub.13/15 acrylate, to a method for preparing the polyacrylate by free-radical polymerization of the C.sub.13/15 acrylate, and to a method for preparing a lubricant by contacting the polyacrylate to a base oil.

Claims

1.-15. (canceled)

16. A lubricant comprising a polyacrylate which contains a C.sub.13/15 acrylate in polymerized form, where the C.sub.13/15 acrylate comprises at least 70 wt % of linear and branched C.sub.13 and C.sub.15 alkyl (meth)acrylates.

17. The lubricant according to claim 16 where the linear and branched C.sub.13 and C.sub.15 alkyl groups of the C.sub.13/15 acrylate are derived from a C.sub.13/15 alkanol obtained by reacting a monoolefin mixture of C.sub.12 and C.sub.14 olefins with carbon monoxide and hydrogen.

18. The lubricant according to claim 16 where the C.sub.13/15 acrylate comprises less than 5 wt % of each C.sub.12, C.sub.14 and C.sub.16 alkyl (meth)acrylate.

19. The lubricant according to claim 16 where the C.sub.13/15 acrylate comprises a weight ratio of branched C.sub.13 and C.sub.15 alkyl to linear C.sub.13 and C.sub.15 alkyl in a range from 3:1 to 1:3.

20. The lubricant according to claim 16 where the C.sub.13/15 acrylate comprises at least 40 wt % of branched C.sub.13 and C.sub.15 alkyl groups.

21. The lubricant according to claim 16 where the C.sub.13/15 acrylate comprises 35 to 85 wt % of linear and branched C.sub.13 alkyl groups.

22. The lubricant according to claim 16 where the C.sub.13/15 acrylate comprises 15 to 50 wt % of branched C.sub.13 alkyl groups.

23. The lubricant according to claim 16 where the C.sub.13/15 acrylate comprises 20 to 60 wt % of linear C.sub.13 alkyl groups, 10 to 50 wt % of branched C.sub.13 alkyl groups, 3 to 30 wt % of linear C.sub.15 alkyl groups, and 3 to 30 wt % of branched C.sub.15 alkyl groups.

24. The lubricant according to claim 16 where the polyacrylate comprises at least 50 wt % of the C.sub.13/15 acrylate.

25. The lubricant according to claim 16 where the polyacrylate comprises up to 25 wt % of a comonomer selected from C.sub.1-C.sub.18 alkyl (meth)acrylate.

26. The lubricant according to claim 16 comprising 0.1 to 40 wt % of the polyacrylate.

27. A polyacrylate as defined in claim 16.

28. A C.sub.13/15 acrylate as defined in claim 16.

29. A method for preparing the polyacrylate as defined in claim 16 by free-radical polymerization of the C.sub.13/15 acrylate as defined in claim 16.

30. A method for preparing a lubricant by contacting the polyacrylate as defined in claim 16 to a base oil.

Description

EXAMPLES

Example 1—Alcohol Preparation

[0142] A C.sub.13/15 alkanol was prepared according to WO 2002/00580. The obtained C.sub.13/15 alkanol was analyzed by GC. The average composition from several preparations was as follows:

[0143] 30.9 wt % linear C.sub.13 alkanol

[0144] 37.6 wt % branched C.sub.13 alkanol

[0145] 13.1 wt % linear C.sub.15 alkanol

[0146] 17.9 wt % branched C.sub.15 alkanol

[0147] The amount of C.sub.12 alkanol, C.sub.14 alkanol and C.sub.16 alkanol was each below 1 wt %.

Example 2—Monomer Preparation

[0148] In a stirred 4 L reactor cyclohexan (1490 g), C.sub.13/15 alkanol from Example 1 (1935 g), hydroquinone monomethyl ether MeHQ (2,3 g), hypophosphoric acid 50% in water (5,8 g) and Cu(II) chloride solution (20% ig, 1,35 g) were added. Then methacrylic acid (968 g, stabilized with 200 ppm MeHQ), p-toluolsulfonic acid monohydrate (51,4 g) were added and heating started. At a sump temperature of 81 to 100° C. water went over. After 6,3 h the reaction was stopped. The reaction mixutre was cooled down and extraction with NaOH solution and with water. After phase separation 250 mg MeHQ were added to the organic phase and concenentrated in vacuum. 2451 g of methacrylic ester of the C.sub.13/15 alkanol were obtained with a purity of >98 GC-Fl%.

Example 3—Polymerization

[0149] 66.7 g of the monomer from Example 2 and 1.8 g n-dodecyl-mercaptane (DDM) were mixed in a flask and heated up to 95° C. resulting in a colorless, clear solution. 25.33 g of a 9% solution of tert-butylperoctoate (TBPEH) in paraffinic oil was prepared and continuously fed within 2 hours. Separately, but parallel a mixture of 133.33 g of the C.sub.13/15 acrylate from Example 2 and 3.6 g n-dodecylmercaptane was fed continuously to the flask for 2 hours. The prepared polymer solution was then stirred without any further initiator feed at 95° C. for 60 min and at 130° C. for 30 min. The obtained 90% polymer solution is allowed to cool down to room temperature forming a colorless, viscous liquid.

[0150] Polymers were prepared varying amount of tert-butylperoctoate and dodecylmercaptane amount. The reaction temperature and solvent were kept constant.

[0151] The viscosity was determined (Brookfield, at 100° C.). The molecular weight Mw was determined by GPC analysis (polystyrene standard, detector: DRI Agilent 1100 UV Agilent 1100 VWD [254 nm]) with tetrahydrofuran+0.1% trifluoracetic acid eluent (flow rate: 1 ml/min) at a concentration of 2 mg/ml on a PLgel MIXED-B column.

TABLE-US-00001 TABLE 1a Polymer # TBPEH/g DDM/g KV100/cSt Mw/g/mol PDI 1 2.28 5.39 512 21 900 1.9 2 2.28 5.65 486 21 000 1.9 3 2.28 6.06 448 19 800 1.8 4 2.28 6.73 378 17 600 1.8

[0152] Comparative polymers were synthesized from the methacrylate monomers in Table 1b according to the above procedure and characterized as summarized in Table 1b. The following monomers were used:

[0153] TDN: Methacrylate based on Isotridecanol N from BASF SE which contained at least 99% of tridecanol isomers.

[0154] Lialchem 25/75: Methacrylate of Lialchem® 25/75 from Sasol, which contained an alkanol distribution of 22% C12, 32% C13, 29% C14, 17% C15 and 0.5% C16 or higher, and an overall content of linear alcohols of 77 wt %.

[0155] Neodol 25: Methacrylate of Neodol® 25 from Shell Chemicals, which contained an alkanol distribution of <1% C11 or lower, 21% C12, 29% C13, 25% C14, 25% C15 and <1% C16 or higher.

[0156] Lial 125: Methacrylate of Lial® 125 from Sasol, which contained an alkanol distribution of <1% of C11 and lower, 19-25% C12, 28-34% C13, 27-33% C14, 15-21% C15 and <1.5% C16 or higher, and an overall content of linear alcohols of 43 wt %.

TABLE-US-00002 TABLE 1b Comparative Polymers Polymer Methacrylate TBPEH/ DDM/ KV100/ Mw/ # of g g cSt g/mol PDI C1 TDN 2.28 5.39 1068 19 100 1.9 C2 Lialchem 5/75 3.60 6.73 298 17 700 1.9 C3 Lialchem 5/75 3.60 5.39 520 26 600 2.0 C4 Neodol 25 3.60 5.39 376 22 800 2.0 C5 Lial125 2.28 4.71 587 21 400 2.0 C6 Lial125 2.28 6.06 411 17 100 1.9

Example 4—Low Temperature Viscosity of Oil Blends

[0157] Oil blends were prepared with the following composition in Table 2. The treat rate of the polyacrylate is given in the Table 3. A group I base oil (KV 40 about 30 mm.sup.2/s, ASTM D445, pour point below −15° C., viscosity index >95) was added at the end to balance to 100%.

TABLE-US-00003 TABLE 2 Component Amount (wt. %) HiTEC ® 369 (gear oil additive package, Afton 6.00 Chemical) Irgaflo ® 649 P (pour point depressant, BASF 0.2 Corp.) SpectraSyn ® 4 (Polyalphaolefinn, group IV 15 base oil, ExxonMobil) Polyacrylate from Example 3 cf. Treat Rate Group I base oil (ExxonMobil) Balanced

[0158] The kinematic viscosity at 100° C. (“KV100”) was determined according to ASTM D445. The low temperature viscosity (“LTB at −40° C.”) was determined by rotational viscometer ASTM D2983 at −40° C. and the results are summarized in Table 3 and 4.

[0159] The data showed that the polyacrylates according to our invention have desirable lower viscosity at low temperatures compared to other polymers.

TABLE-US-00004 TABLE 3 Treat rate KV 100 LTB at −40° C. Blend # Polymer # [%] [cSt] [cSt] B1 1 26 16.6 94800 B2 2 26 16.0 97000 B3 2 27.5 17.0 110000 B4 3 27.5 16.7 104000 B5 4 26 14.6 85600 B6 4 27.5 15.5 97600

TABLE-US-00005 TABLE 4 Comparative Data Treat rate KV 100 LTB at −40° C. Blend # Polymer # [%] [cSt] [cSt] BC1 C1 22 14.5 522000 BC2 C1 24 16.0 2000000 BC3 C2 28.5 16.1 2000000 BC4 C3 23 16.4 2000000 BC5 C4 26 16.3 2000000 BC6 C5 25.5 16.7 123000 BC7 C5 26.5 17.4 132000 BC8 C6 26 14.9 111000 BC9 C6 27 15.5 115000

Example 5—Copolymers

[0160] The methacrylic ester of the C.sub.13/15 alkanol of example 2 was copolymerized with 10 wt % methyl methacrylate as follows.

[0161] 70.0 g of the monomer from Example 2, 6.67 g methyl methacrylate and 2.16 g n-dodecyl-mercaptane in 72 g Nynas® T3 (low viscosity hydrotreated naphthenic API Group V base oil) were mixed in a flask and heated up to 95° C. resulting in a colorless, clear solution. 26 g of a 9% solution of tert-butylperoctoate in paraffinic oil was prepared and continuously fed within 2 hours. Separately, but parallel a mixture of 120 g of the C.sub.13/15 acrylate from Example 2, 13.3 g methyl methacrylate and 4.3 g n-dodecylmercaptane and 115 g of a 9% solution of tert-butylperoctoated was fed continuously to the flask for 2 hours. The prepared polymer solution was then stirred without any further initiator feed at 95° C. for 60 min and at 130° C. for 30 min. The obtained 60% polymer solution is allowed to cool down to room temperature forming a colorless, viscous liquid.

[0162] The polymers were analyzed as decribed in Example 3, and the results are summarized in Table 5.

TABLE-US-00006 TABLE 5 Polymer # TBPEH/g DDM/g KV100/cSt Mw/g/mol PDI 5 6.92 6.48 58 14 600 2.2 6 6.92 8.10 42 12 100 2.1 7 6.92 4.06 66 17 600 2.3

Example 6—Low Temperature Viscosity of Oil Blends

[0163] Oil blends were prepared with the following composition in Table 6 with the polyacrylate from Example 3. The treat rate of the polyacrylate is given in the Table 7.

TABLE-US-00007 TABLE 6 Oil blends with given SAE J 306 viscosity grades, amount in wt. % B7 B8 B9 Component 75W-80 75W-85 80W-140 HiTEC ® 369 (gear oil additive package, 6.0 6.0  6.0 Afton Chemical) Irgaflo ® 649 P (pour point depressant, 0.5 0.5 — BASF Corp.) Chevron Neutral Oil 220R (Group II — — 30.9 parrafinic base oil, KV40 41 cSt, VI 102) Chevron Neutral Oil 600R (Group II — — 32.4 parrafinic base oil, KV40 106 cSt, VI 102) Yubase 4 (Group III base oil, KV40 19.6 21.0 17.5 — cSt, VI 122) Yubase 6 (Group III base oil, KV40 36.8 60.0 57.4 — cSt, VI 131)

[0164] The oil blends were tested as described in Example 4 and the results are summarized in Table 7.

TABLE-US-00008 TABLE 7 Treat LTB Blend Polymer rate KV 100 at −40° C. # SAE # [%] [cSt] [cSt] B7 75W-80 2 12.5 13.07 75000 B8 75W-85 2 18.6 10.00 51000 B9 80W-140 2 30.7 29.80 120000