CN113717225A - 一种高粘度磷酸酯及其制备方法、用途和组合物 - Google Patents
一种高粘度磷酸酯及其制备方法、用途和组合物 Download PDFInfo
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 49
- 239000010452 phosphate Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title abstract description 27
- 239000010720 hydraulic oil Substances 0.000 claims abstract description 26
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003063 flame retardant Substances 0.000 claims abstract description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims abstract description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 28
- -1 phosphate ester Chemical class 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002199 base oil Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- 230000009970 fire resistant effect Effects 0.000 claims description 5
- 229910019213 POCl3 Inorganic materials 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical group 0.000 claims description 4
- 239000013556 antirust agent Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl chloride Substances ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- VXZJUYUVOQZBNU-UHFFFAOYSA-N phosphoric acid 1,2-xylene Chemical compound P(=O)(O)(O)O.CC1=C(C=CC=C1)C.CC1=C(C=CC=C1)C.CC1=C(C=CC=C1)C VXZJUYUVOQZBNU-UHFFFAOYSA-N 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 239000000047 product Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 11
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000001965 increasing effect Effects 0.000 description 9
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000002269 spontaneous effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000196 viscometry Methods 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000326 densiometry Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000011545 laboratory measurement Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3229—Esters of aromatic acids (P-C aromatic linkage)
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/026—Butene
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
- C10M2223/0415—Triaryl phosphates used as base material
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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Abstract
Description
技术领域
本发明属于高温磷酸酯抗燃液压油技术领域,具体涉及一种高粘度磷酸酯及其制备方法、用途和组合物。
背景技术
磷酸酯抗燃液压油被广泛应用于电力、军事、飞机液压***,具有极强的抗燃性能,在与高温热源以及明火有接触的液压***中,具有不可替代的地位。随着大容量、高参数的汽轮机组的大量使用,火力电厂单机容量已达800MW以上,这对磷酸酯抗燃液压油的抗燃性能、高温抗磨性能、高温抗氧化性能等提出了更高的要求。特别是使用温度的升高,需要使用高粘度液压油才能确保在摩擦部位形成良好的润滑油膜。
目前由于广泛使用的磷酸酯抗燃液压油为ISO VG32和VG46的磷酸酯抗燃液压油,存在以下问题:①抗燃性能不佳,自燃点普遍在550℃以下;②在高温的使用条件下油膜强度不够,存在磨损大、会导致设备寿命短的问题;③抗氧化性能差,老化变质快,换油期短。为解决磷酸酯抗燃液压油的上述缺点,需要使用粘度更高的磷酸酯抗燃液压油。但由于磷酸酯空间位阻问题,工业化的磷酸酯基础油很难达到ISO VG46以上。目前,为增加磷酸酯抗燃液压油的粘度,主要采取加入增粘剂的办法。然而由于磷酸酯的结构特点以及磷酸酯抗燃液压油的指标要求,现有的增粘剂不能满足要求,如常用的PMA(聚甲基丙烯酸酯)类、OCP类、PIB类增粘剂,与磷酸酯相容性差,会导致密度减小、空气释放值变差、自燃点降低等问题。
为解决目前增粘剂存在的问题,申请人发明一种高性能磷酸酯抗燃液压油增粘剂,具有与磷酸酯结构相似、相容性好,且能提高磷酸酯抗燃液压油氧化安定性和高温抗磨性等特点,可满足高温液压***的使用要求。
发明内容
本发明的目的在于克服目前广泛使用的增粘剂与磷酸酯相容性差导致的密度减小、空气释放值变差、自燃点降低等问题。用此磷酸酯作为增粘剂可以配制不同粘度等级的磷酸酯抗燃液压油,具有相容性好、自燃点高、氧化安定性和高温抗磨性能好等特点,可满足高温高压液压***的使用要求。
本发明为了实现上述技术目的,提供如下技术方案:一种高粘度磷酸酯,结构如式(I)所示:
式I中,R1、R2、R3、R4分别独立地选自被1-5个甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基取代的苯基或未被取代的苯基;
R为C2-20的亚烷基。
进一步地,所述R1、R2、R3、R4至少有一个为4-异丙基苯基;
再进一步地,所述R1、R2、R3、R4至多有三个为4-异丙基苯基;
进一步地,所述R1、R2、R3、R4分别独立地选自苯基、4-甲基苯基、4-异丙基苯基、4-叔丁基苯基;
本发明还提供了如上所述的磷酸酯的制备方法,具体步骤如下:
POCl3与二羟基化合物在全氟磺酸树脂存在的条件下反应得到式(II)化合物;
式(II)化合物与单羟基化合物在全氟磺酸树脂存在的条件下反应得到式(I)化合物,各基团定义如前所述。
进一步地,步骤a具体为POCl3与二羟基化合物在全氟磺酸树脂存在的条件下加热至90-100℃反应1-2h,随后升温至110-130℃反应1-2h,得到(II)化合物;
步骤b具体为式(II)化合物与单羟基化合物在全氟磺酸树脂存在的条件下加热至140-150℃反应2-3h,随后升温至150-160℃反应1-2h,经后处理得到(I)化合物。
本发明还提供了如上所述的高粘度磷酸酯用于抗燃液压油组合物的用途。
进一步地,所述高粘度磷酸酯作为磷酸酯抗燃液压油中增粘剂的用途。
本发明还提供了一种抗燃液压油包括如权利要求1-3任一项所述的高粘度磷酸酯。
进一步地,所述抗燃液压油具有如下组成:
基础油:50-100份;
抗氧剂:0.1-1份;
防锈剂:0.1-0.5份;
抗腐蚀剂:0.01-0.1份;
如权利要求1-3任一项所述的高粘度磷酸酯:1-50份;
所述基础油为叔丁基化磷酸三苯酯或磷酸三(二甲苯)酯或二者的混合物;
所述抗氧剂为胺型抗氧剂或酚型抗氧剂或二者的混合物;
更进一步地,所述胺型抗氧剂为T534型;所述酚型抗氧剂为T501型、L135型或二者的混合物;
更进一步地,所述防锈剂为T705型或T711型或两者的混合物;所述抗腐蚀剂为T706型。
本发明还提供了如上所述的抗燃液压油的制备方法,将各组分按配比混合,加入活性白土和/或活性炭并加热至145-155℃并保温1-3小时,过滤得产品。
进一步地,所述活性白土的用量为混合物总重量的5%;所述活性炭的用量为混合物总重量的1%。
由于采用了以上技术,本发明与现有技术相比,其显著优点为:
1)本发明的高粘度磷酸酯与常用磷酸酯基础油有极好的相容性,同时具有极佳的抗燃性和增粘性,能有效克服目前广泛使用的增粘剂与磷酸酯相容性差导致的密度减小、空气释放值变差、自燃点降低等问题;
2)使用本发明的高粘度磷酸酯制备得到的的磷酸酯抗燃液压油自燃点高(大于600℃)、抗氧化性能强(具有较强的酸捕捉能力、可有效抑制酸值增加,且能保持液压油体积电阻率稳定),能显著提高抗磨极压性能,可有效延长设备使用寿命。
具体实施方式
为了使本发明的技术方案及优点更加清楚明白,以下结合实施例对本发明进行进一步详细说明。
实施例1
(1)将5molPOC13(766.65g)、1mol新戊二醇(104.15g)、1g全氟磺酸树脂(江阴南大合成化学有限公司生产的全氟磺酸树脂HNF-5W),一次性加入到装有搅拌器、温度计、回流管的2L四口烧瓶中;然后在30min内将反应温度升到95~100℃,在此温度下保持1h,之后在35~45min内升至110~130℃,反应2h。反应结束后,在-0.01MPa的真空度下蒸馏出过量的POCl3。
(2)在蒸馏后的产物中补加1g全氟磺酸树脂,在105~110℃时逐步加入572g4-异丙基苯酚(过量5%),在30min内加完。加完后将温度升高为140~150℃,反应3h,然后再升温至150~160℃反应2h。将反应后的产物真空蒸馏除去未反应的新戊二醇和低沸点产物,得到粗产品;然后往产品中加入适量的1,2一二氯乙烷,过滤除去全氟磺酸树脂,再用2%Na0H水溶液中和至弱碱性,最后用去离子水洗至中性。将有机层分离出来后真空蒸馏除去溶剂和水,得到粘稠状磷酸酯产品,收率97.1%,纯度99.2%,LC-MS(ESI):m/z 672[M+H]+。基本性能见表1。
实施例2
(1)将5molPOC13(766.65g)、1mol新戊二醇(104.15g)、1g全氟磺酸树脂(江阴南大合成化学有限公司生产的全氟磺酸树脂HNF-5W),一次性加入到装有搅拌器、温度计、回流管的2L四口烧瓶中;然后在30min内将反应温度升到95~100℃,在此温度下保持1h,之后在35~45min内升至110~130℃,反应2h。反应结束后,在-0.01MPa的真空度下蒸馏出过量的POCl3。
(2)在蒸馏后的产物中补加与1g全氟磺酸树脂,在105~110℃时逐步顺序加入272.38g4-异丙基苯酚和227.1g对甲苯酚(过量5%),在30min内加完。加完后将温度升高为140~150℃,反应3h,然后再升温至150~160℃反应2h。将反应后的产物真空蒸馏除去未反应的新戊二醇和低沸点产物,得到粗产品;然后往产品中加入适量的1,2一二氯乙烷,过滤除去全氟磺酸树脂,再用2%Na0H水溶液中和至弱碱性,最后用去离子水洗至中性。将有机层分离出来后真空蒸馏除去溶剂和水,得到粘稠状磷酸酯产品,LC-MS(ESI):m/z 616[M+H]+。基本性能见表1。
实施例3
(1)将5molPOC13(766.65g)、1mol新戊二醇(104.15g)、1g全氟磺酸树脂(江阴南大合成化学有限公司生产的全氟磺酸树脂HNF-5W),一次性加入到装有搅拌器、温度计、回流管的2L四口烧瓶中;然后在30min内将反应温度升到95~100℃,在此温度下保持1h,之后在35~45min内升至110~130℃,反应2h。反应结束后,在-0.01MPa的真空度下蒸馏出过量的POCl3。
(2)在蒸馏后的产物中补加1g全氟磺酸树脂,在105~110℃时顺序逐步加入108g对甲苯酚、136.19g 4-异丙基苯酚、150.22g对叔丁基苯酚的混合物,加毕加入98.7克苯酚(过量5%)的混合物,总加料时间在30min内加完。加完后将温度升高到140~150℃,反应3h,然后再升温至150~160℃反应2h。将反应后的产物真空蒸馏除去未反应的新戊二醇和低沸点产物,得到粗产品;然后往产品中加入适量的1,2一二氯乙烷,过滤除去全氟磺酸树脂,再用2%Na0H水溶液中和至弱碱性,最后用去离子水洗至中性。将有机层分离出来后真空蒸馏除去溶剂和水,得到粘稠状磷酸酯产品(HPLC分析主要产物为I-1、少量为I-2),收率93.1%,纯度99.6%。基本性能见表1。
实施例4
(1)将5molPOC13(766.65g)、1mol新戊二醇(104.15g)、1g全氟磺酸树脂(江阴南大合成化学有限公司生产的全氟磺酸树脂HNF-5W),一次性加入到装有搅拌器、温度计、回流管的2L四口烧瓶中;然后在30min内将反应温度升到95~100℃,在此温度下保持1h,之后在35~45min内升至110~130℃,反应2h。反应结束后,在-0.01MPa的真空度下蒸馏出过量的POCl3。。
(2)在蒸馏后的产物中补加1g全氟磺酸树脂,在105~110℃时顺序逐步加入136.19g4-异丙基苯酚和335.3g对甲苯酚(过量5%),在30min内加完。加完后将温度升高到140~150℃,反应3h,然后再升温至150~160℃反应2h。将反应后的产物真空蒸馏除去未反应的新戊二醇和低沸点产物,得到粗产品;然后往产品中加入适量的1,2一二氯乙烷,过滤除去全氟磺酸树脂,再用2%Na0H水溶液中和至弱碱性,最后用去离子水洗至中性。将有机层分离出来后真空蒸馏除去溶剂和水,得到粘稠状磷酸酯产品,收率92.5%,纯度99.1%,LC-MS(ESI):m/z 588[M+H]+。基本性能见表1。
实施例5
(1)将5molPOC13(766.65g)、1mol新戊二醇(104.15g)、1g全氟磺酸树脂(江阴南大合成化学有限公司生产的全氟磺酸树脂HNF-5W),一次性加入到装有搅拌器、温度计、回流管的2L四口烧瓶中;然后在30min内将反应温度升到95~100℃,在此温度下保持1h,之后在35~45min内升至110~130℃,反应2h。反应结束后,在-O.01MPa的真空度下蒸馏出过量的POCl3。。
(2)在蒸馏后的产物中补加1g全氟磺酸树脂,在105~110℃时加入454.2g对甲苯酚(过量5%),30min内加完。加完后将温度升高到140~150℃,反应3h,然后再升温至150~160℃反应2h。将反应后的产物真空蒸馏除去未反应的新戊二醇和低沸点产物,得到粗产品;然后往产品中加入适量的1,2一二氯乙烷,过滤除去全氟磺酸树脂,再用2%Na0H水溶液中和至弱碱性,最后用去离子水洗至中性。将有机层分离出来后真空蒸馏除去溶剂和水,得到粘稠状磷酸酯产品,收率89.9%,纯度98.7%,LC-MS(ESI):m/z 560[M+H]+。基本性能见表1。
实施例6
将实施例1-5制备得到的磷酸酯产品进行性能测试,测试结果见表1。
表1增粘剂性能测试结果
项目 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 |
<sup>*</sup>40℃运动粘度,mm<sup>2</sup>/s | 3113.5 | 2219.3 | 2737.1 | 2536.6 | 1093.2 |
闪点,℃ | 301 | 312 | 307 | 310 | 257 |
*按照《GB/T265》中记载的石油产品运动黏度测定法和动力黏度计算法进行测试。
实施例7-14
将基础油、添加剂、增粘剂及活性白土(按总量的5%)、活性炭(按总量的1%)加入调和釜中,加热热到120℃±5℃,恒温2小时,然后过滤得产品。
配制方法如上,配方组成见表。
表2实施例7-14的具体配方组成
组成(份) | 实施例7 | 实施例8 | 实施例9 | 实施例10 | 实施例11 | 实施例12 | 实施例13 | 实施例14 |
BPDP | 78 | 76 | 78 | 78 | -- | 42 | 77 | 79 |
TXP | -- | -- | -- | -- | 87 | 42 | -- | -- |
实施例1 | 22 | -- | -- | -- | -- | -- | -- | -- |
实施例2 | -- | 24 | -- | -- | -- | -- | -- | -- |
实施例3 | -- | -- | 22 | -- | -- | -- | -- | -- |
实施例4 | -- | -- | -- | 22 | 13 | 16 | -- | -- |
实施例5 | -- | -- | -- | -- | -- | -- | 10 | 13 |
PIB(PB2400) | -- | -- | -- | -- | -- | -- | 13 | -- |
PMA(V8-310) | -- | -- | -- | -- | -- | -- | -- | 8 |
抗氧剂L135 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
防锈剂T711 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
抗腐蚀剂T706 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
实施例7-14的性能测试结果见表3。
表3实施例7-14的性能测试结果
表中相关的试验方法标准为:40℃运动粘度:GB/T265(石油产品运动黏度测定法和动力黏度计算法);
自燃点:DL 706(电厂用抗燃油自燃点测定方法);
体积电阻率:DL/T 421(电为用油体积电阻率测定法);
空气释放值:SH/T 0308(润滑油空气释放值测定法);
20℃密度:GB/T 1884(原油或液体石油产品密度实验室测定法(密度计法);
磨斑直径:SH/T 0189(润滑油抗磨性能测试法(四球机法);
氧化试验:EN 14832(氧化安定性测定方法)。
从表2可以看出:实施例自燃点高、体积电阻率大、空气释放值小,抗磨性能好,具有更好的抗氧化性能(氧化试验后酸值增加很小,对铜和钢腐蚀小)。
上述实施例仅为本发明的优选技术方案,而不应视为对于本发明的限制,本发明的保护范围应以权利要求记载的技术方案,包括权利要求记载的技术方案中技术特征的等同替换方案为保护范围,即在此范围内的等同替换改进,也在本发明的保护范围之内。
Claims (10)
5.根据权利要求4所述的制备方法,其特征在于,步骤a具体为POCl3与二羟基化合物在全氟磺酸树脂存在的条件下加热至90-100℃反应1-2h,随后升温至110-130℃反应1-2h,得到(II)化合物;
步骤b具体为式(II)化合物与单羟基化合物在全氟磺酸树脂存在的条件下加热至140-150℃反应2-3h,随后升温至150-160℃反应1-2h,经后处理得到(I)化合物。
6.如权利要求1-3任一项所述的高粘度磷酸酯用于抗燃液压油组合物的用途。
7.一种抗燃液压油,其特征在于,包括如权利要求1-3任一项所述的高粘度磷酸酯。
8.如权利要求7所述的抗燃液压油,其特征在于,所述抗燃液压油具有如下组成:
基础油:50-100份;
抗氧剂:0.1-1份;
防锈剂:0.1-0.5份;
抗腐蚀剂:0.01-0.1份;
如权利要求1-3任一项所述的高粘度磷酸酯:1-50份;
所述基础油为叔丁基化磷酸三苯酯和/或磷酸三(二甲苯)酯;
所述抗氧剂为胺型抗氧剂和/或酚型抗氧剂。
9.一种如权利要求7所述的抗燃液压油的制备方法,其特征在于,将各组分按配比混合,加入活性白土和/或活性炭并加热至145-155℃并保温1-3小时,过滤得产品。
10.如权利要求8所述的制备方法,其特征在于,所述活性白土的用量为混合物总重量的5%;所述活性炭的用量为混合物总重量的1%。
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