CN102753709B - 水系热处理液组合物 - Google Patents
水系热处理液组合物 Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 238000010438 heat treatment Methods 0.000 title claims abstract description 49
- 239000007788 liquid Substances 0.000 title abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 18
- 239000013556 antirust agent Substances 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 9
- 230000000171 quenching effect Effects 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 10
- 229920000223 polyglycerol Polymers 0.000 abstract 2
- 230000002265 prevention Effects 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 38
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 229920001515 polyalkylene glycol Polymers 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003999 initiator Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000007669 thermal treatment Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- -1 carboxylate salt Chemical class 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910000617 Mangalloy Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- DRLNNBXBGGRLDJ-UHFFFAOYSA-N decanedioic acid;potassium Chemical compound [K].OC(=O)CCCCCCCCC(O)=O DRLNNBXBGGRLDJ-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
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- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 2
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- FBUKVWPVBMHYJY-UHFFFAOYSA-M nonanoate Chemical compound CCCCCCCCC([O-])=O FBUKVWPVBMHYJY-UHFFFAOYSA-M 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- QPTBLKXIIYJZBP-UHFFFAOYSA-N 2-aminoethanol;dodecanedioic acid Chemical compound NCCO.OC(=O)CCCCCCCCCCC(O)=O QPTBLKXIIYJZBP-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- GJBRTCPWCKRSTQ-UHFFFAOYSA-N decanedioic acid Chemical compound OC(=O)CCCCCCCCC(O)=O.OC(=O)CCCCCCCCC(O)=O GJBRTCPWCKRSTQ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000569 multi-angle light scattering Methods 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
- C21D1/60—Aqueous agents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/005—Dendritic macromolecules
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- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/081—Inorganic acids or salts thereof containing halogen
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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Abstract
本发明提供具有高的冷却性能和耐冷却不均性能、同时防锈性能良好的水系热处理液组合物。水系热处理液组合物的特征在于:配合超支化型聚甘油而成。另外,超支化型聚甘油的质均绝对分子量优选5,000以上500,000以下。若使用该水系热处理液组合物进行金属部件的淬火,则具有高冷却性能和耐冷却不均性能,同时可发挥良好的防锈性能。
Description
技术领域
本发明涉及在金属部件的淬火等中使用的水系热处理液组合物。
背景技术
金属部件的淬火中使用的热处理液大致分为油系和水系(水溶液系),广泛使用油系。这是由于,油系热处理液具有适度的冷却性能,淬火变形小,不用担心淬裂产生。
另一方面,对于特别大的金属部件或淬火性差的金属部件,油系热处理液的冷却速度慢,冷却性能不足,因此使用水系热处理液。但是,水系热处理液比油系热处理液的冷却性能高,因此,容易发生冷却不均,可能淬裂。
因此,为了防止淬裂,已知有在水系热处理液中添加水溶性聚合物的组合物。上述水系热处理液组合物中,水溶性聚合物附着于金属部件的表面,阻碍热传递,抑制冷却性能。添加了水溶性聚合物的水系热处理液组合物在工业上得到普及,作为水溶性聚合物,聚亚烷基二醇(PAG)是主流。不过上述水系热处理液组合物的蒸气膜阶段长,因此有容易发生冷却不均的缺点。
因此,有人提出了一种水系热处理液组合物,其中,通过在高分子量的聚亚烷基二醇中添加低分子量的二醇,缩短蒸气膜阶段,使耐冷却不均性能提高 (参照专利文献1)。
另一方面,作为提高耐冷却不均性能的技术,已知长期以来采用食盐水的淬火。食盐水没有蒸气膜阶段,因此具有高冷却性能,同时耐冷却不均性能高,淬裂少(参照非专利文献1)。
现有技术文献
专利文献
专利文献1:日本特开平9-227932号公报
非专利文献
非专利文献1:大和久重雄,“焼割れを考える (对淬裂的探讨) ”,热处理,昭和42年6月,第7卷,第3号,140-144页。
发明内容
发明要解决的课题
但是,专利文献1的水系热处理液组合物的耐冷却不均性能也不一定充分。
另外,非专利文献1的食盐水在热处理后1小时以内这样极短的时间内即生锈,对油槽等设备的腐蚀也显著,因此几乎无法在工业上使用。
因此,本发明的目的在于提供一种水系热处理液组合物,其具有高冷却性能和耐冷却不均性能,同时防锈性能良好。
解决课题的手段
为解决上述课题,本发明提供以下所述的水系热处理液组合物。
[1] 水系热处理液组合物,其特征在于:该水系热处理液组合物是配合超支化型聚甘油而成的。
[2] 上述[1]的水系热处理液组合物,其特征在于:上述超支化型聚甘油的质均绝对分子量为5,000以上500,000以下。
[3] 上述[2]的水系热处理液组合物,其特征在于:上述超支化型聚甘油的质均绝对分子量为5,000以上100,000以下。
[4] 上述[1]-[3]中任一项的水系热处理液组合物,其特征在于:以组合物总量为基准,上述超支化型聚甘油的配合量为3%质量以上30%质量以下。
[5] 上述[1]-[4]中任一项的水系热处理液组合物,其特征在于:该水系热处理液组合物中进一步配合水溶性防锈剂。
[6] 上述[1]-[5]中任一项的水系热处理液组合物,其特征在于:该水系处理液组合物用于以下任意用途:在浸渍淬火、高频淬火,和固溶化处理时的冷却。
发明的效果
本发明的水系热处理液组合物配合超支化型聚甘油,因此具有高冷却性能和耐冷却不均性能,同时可发挥良好的防锈性能。
附图说明
图1是表示以往的聚合物水溶液的冷却性能和耐冷却不均性能的图。
图2是表示本发明的水系热处理液组合物的冷却性能和耐冷却不均性能的图。
图3是用于计算本发明中使用的超支化型聚甘油的支化度的13C-NMR谱的图。
图4是表示本发明的实施例和比较例的水系热处理液组合物的冷却性能的图。
图5是表示比较例的食盐水的冷却性能和耐冷却不均性能的图。
具体实施方案
本发明的水系热处理液组合物(以下可简称为“组合物”)是一种水溶液,其特征在于配合超支化型聚甘油(以下可简称为“HBP-PGR”)而成。
在本发明的组合物中配合的HBP-PGR例如是由缩水甘油的开环聚合得到的下述化学式(1)所示的超支化型聚合物。HBP-PGR在缩水甘油的重复单元上具有分支结构。
[化1]
配合了本发明的HBP-PGR的组合物具有高冷却性能和耐冷却不均性能,同时也具有良好的防锈性能。
使用以往的聚合物水溶液进行淬火时,蒸气膜阶段长,因此容易发生冷却不均。因此搅拌聚合物水溶液来抑制冷却不均的发生。但是,根据金属部件的大小或形状,搅拌效率部分降低。搅拌效率低的部分中,冷却速度相对变慢,因此容易发生冷却不均。这里,冷却不均发生的容易程度可通过有无搅拌带来的冷却时间的差来评价。在以往的聚合物水溶液中,例如如图1所示,冷却时间的差大,因此容易发生冷却不均。
与此相对,本发明的组合物中,例如如图2所述,几乎没有蒸气膜阶段,有无搅拌带来的冷却时间的差几乎没有,因此冷却速度快,可抑制冷却不均的发生(具体实验条件如后所述)。特别是在金属部件大时或形状复杂时,本发明的组合物可发挥高的耐冷却不均性能。
另外,本发明的组合物中,与以往的聚合物水溶液不同,不在金属部件的表面形成聚合物膜,因此可进一步发挥高冷却性能和耐冷却不均性能。
HBP-PGR的配合量,按照组合物总量基准,优选3%质量以上30%质量以下。
如果HBP-PGR的配合量为3%质量以上,则可充分发挥耐冷却不均性能。另一方面,如果HBP-PGR的配合量为30%质量以下,则可以抑制粘性升高,金属部件无需粘性物洗涤工序。
因此,优选的HBP-PGR的配合量范围是5%质量以上15%质量以下。
HBP-PGR的质均绝对分子量优选5,000以上500,000以下。
如果HBP-PGR的质均绝对分子量为5,000以上,则可获得良好的粘性,可充分发挥冷却性能或耐冷却不均性能。另一方面,如果HBP-PGR的质均绝对分子量为500,000以下,则聚合物链难以被切断,可抑制低分子的生成,可充分发挥冷却性能或耐冷却不均性能。
因此,优选的质均绝对分子量的范围是5,000以上100,000以下。
需要说明,HBP-PGR的质均绝对分子量可使用0.2mol/L浓度的NaNO3水溶液作为流动相溶剂,通过尺寸排阻色谱在线-多角度光散射(SEC-MALLS)法测定。
另外,HBP-PGR的支化度为0.40以上0.65以下,优选0.45以上0.55以下。HBP-PGR的支化度可通过以下所述方法测定。
<支化度的测定方法>
测定条件:将200mg聚合物溶解于0.6mL重水
使用装置:100MHz13C-NMR[日本电子株式会社制造,“JEOLJNM-A400II”]
测定条件:带反转门控的13C-NMR测定(nne13C-NMR),脉冲间隔时间7秒,以丙酮作为标准峰(δ:30.89ppm)进行测定。
积分次数:4000次
积分中使用的各峰范围:
·L1:60.75-62.12ppm
·T:62.68-63.35ppm
·L2:72.01-73.38ppm(该峰的积分值包含2个碳的量,因此计算时采取其一半的值)
·D:76.93-79.68ppm;
上述各峰范围以图3的13C-NMR谱表示。
支化度(DB)按照下式(2),由上述各峰的积分值计算。
支化度(DB)=2D/(2D+L1+L2/2)…(2)
[HBP-PGR的制造方法]
HBP-PGR的制造方法是使用BF3络合物作为引发剂,使单体缩水甘油进行开环聚合。此时,作为引发剂使用的BF3络合物例如可举出:BF3·乙基醚络合物[(C2H5)2O·BF3]、BF3·苯酚络合物[(C6H5OH)2·BF3]、BF3·单乙基胺络合物[C2H5NH2·BF3]、BF3·正丁基醚络合物[(n-C4H9)2O·BF3]等。其中,从作为引发剂的性能上看,优选BF3·乙基醚络合物。
该开环聚合中的溶剂可以使用对反应为惰性并可充分溶解引发剂、单体缩水甘油和产物HBP-PGR的有机溶剂,特别优选二氯甲烷。
作为具体的操作,若举出优选的例子说明,如下:在具备搅拌装置和缩水甘油加入装置的反应装置中,加入作为溶剂的二氯甲烷和作为引发剂的BF3·乙基醚络合物,边搅拌该含有引发剂的溶液边缓慢向其中加入缩水甘油。上述BF3·乙基醚络合物的加入量是:对于每1L溶剂,为1毫摩尔以上10毫摩尔以下,优选2毫摩尔以上6毫摩尔以下。
另外,缩水甘油的加入速度是:对于每1L溶剂,为0.05摩尔/小时以上1.0摩尔/小时以下,优选0.1摩尔/小时以上0.5摩尔/小时以下。聚合温度优选-30℃以上10℃以下,更优选-20℃以上0℃以下。
从HBP-PGR的收率方面考虑,缩水甘油的全部加入量是:相对于1摩尔BF3·乙基醚络合物,为300摩尔以上1,800摩尔以下,优选400摩尔以上1,600摩尔以下。
另外,关于搅拌条件,可根据反应装置的大小或搅拌装置的形状等选择最佳条件。加入缩水甘油后,进一步在上述聚合温度下进行后搅拌,继续进行聚合。全部聚合时间受聚合温度、引发剂或缩水甘油的加入量等左右,不能一概而论,通常为20小时以上50小时以下。
如上所述,进行开环聚合,通过适当选定上述各条件,HBP-PGR的质均绝对分子量可控制,同时可以再现性良好地获得HBP-PGR。
需要说明,该开环聚合反应中,在反应体系中单体少的条件下,容易发生分子内环化(回咬(backbiting))。因此,在缩水甘油的加入速度过慢时或聚合时间过长时,容易发生分子内环化,导致低分子量化或收率的降低。
反应结束后,例如通过进行下述操作,可以高效率地获得以开环聚合生成的HBP-PGR。
即,通过氨水等使反应终止,然后馏去溶剂,将残渣溶解于甲醇,用丙酮再沉淀,由此可以以高纯度获得HBP-PGR。
优选本发明的组合物中进一步配合水溶性防锈剂。从防锈性能的提高与经济性的平衡等方面考虑,以组合物总量为基准,水溶性防锈剂的配合量优选0.01%质量以上5%质量以下,更优选0.03%质量以上1%质量以下。
水溶性防锈剂可举出:辛酸盐、壬酸盐等脂族单羧酸盐,或异壬酸盐、新癸酸盐等脂族分支羧酸盐,辛二酸(软木酸)盐、癸二酸(皮脂酸)盐、十二烷二酸等的脂族二羧酸盐,例如优选使用癸二酸钾、十二烷二酸乙醇胺盐等可优选使用。需要说明,水溶性防锈剂还可以是芳族羧酸盐。
另外,水溶性防锈剂还可优选使用单羟基单乙基哌嗪等的哌嗪衍生物等。
本发明的组合物中可进一步配合热处理液中常用的添加剂,例如抗氧化剂和清净分散剂等。
本发明的组合物在金属部件的热处理中可发挥优异的冷却性能、耐冷却不均性能和防锈性能,例如作为对碳钢、镍-锰钢、铬-钼钢、锰钢等各种合金钢的热处理液适合地使用。
另外,使用本发明的组合物对钢材等金属部件进行热处理时,将热处理液组合物的温度设定为通常的热处理温度(40℃左右)。需要说明,在控制了冷却性能时,也可以使组合物的温度在100℃以下尽可能地提高。
本发明的组合物具有高冷却性能和耐冷却不均性能,同时发挥防锈性能,因此可以作为在浸渍淬火、高频淬火、铝等固溶化处理时的冷却等中使用的热处理液适合地使用。
实施例
接着,通过实施例、比较例进一步详细说明本发明,但本发明并不受这些例子的任何限制。具体来说,按照以下方法评价水系热处理液组合物的冷却性能、耐冷却不均性能和防锈性能。
[实施例1、2和比较例1至比较例5]
将以下所示配合剂以规定量配合到水中,调制水系热处理液组合物,制成试样液。配合组成如表1所示。
(1)(配合剂)
(1.1)热处理剂
超支化型聚甘油(HBP-PGR):质均绝对分子量(Mw)=10,000,分子量分散度(Mw/Mn)=3.08,支化度(BD)=0.51
聚亚烷基二醇(PAG):质均绝对分子量(Mw)=40,000
乙二醇单丁基醚和丙二醇:市售商品
(1.2)水溶性防锈剂
癸二酸钾和单羟基单乙基哌嗪:市售商品
(1.3)食盐:市售商品。
(2)质均绝对分子量(Mw)的测定
HBP-PGR和PAG的质均绝对分子量,按照下述装置和条件、通过尺寸排阻色谱在线-多角度光散射(SEC-MALS)法测定。需要说明,使用聚苯乙烯作为标准品。
分离柱:使用2根Tosoh TSKgel GMPWXL柱(线性,7.5mm×600mm;排阻限,5×107)。
柱温:40℃
流动相溶剂:0.2mol/L浓度NaNO3水溶液
流动相流速:1.0mL/分钟
试样浓度:3g/mL
注入量:100μL
检测器1:多角度光散射检测器(Wyatt公司制造,“DAWN8”)
检测器2:粘度检测器(Wyatt公司制造,“Viscostar”)
检测器3:折射率(RI)检测器(Wyatt公司制造,“OptilabrEX”)
(3)平均分子量分布的测定(质均绝对分子量(Mw)/数均分子量(Mn),Mw和Mn是标准聚苯乙烯换算值)
采用上述(2)的装置和条件,通过SEC-MALLS法获得。
(4)支化度(DB)的测定
按照本说明书所述方法求出。
[表1]
[评价方法]
按照以下所示方法,对于上述各试样液评价冷却性能、耐冷却不均性能、防锈性能。
<冷却性能>
按照JIS K 2242的冷却性能测定方法评价。即,在不搅拌液温40℃的试样液的状态下,测定铸造物由800℃至150℃冷却的时间(秒),通过该冷却时间评价冷却性能。
<耐冷却不均性能>
在不搅拌液温40℃的试样液的状态下,以铸造物由800℃至150℃冷却的时间(秒)为基准,在将液温40℃的试样液以流速10cm/秒搅拌的状态下,测定铸造物由800℃至150℃冷却的时间,通过与后者的冷却时间的差来评价耐冷却不均性能。
<防锈性能>
按照DIN 51360-12-A评价。即,将2g铸造物碎屑置于在皿内的滤纸上,滴加2ml试样液,评价放置2小时后的状态。防锈性能以以下所示的5阶段的数值表示
0:无锈
1:有锈的痕迹(点状锈产生3处以下)
2:稍有锈(点状锈产生4处以上)
3:中度锈(铸造物全体上产生点状锈)
4:重度锈(铸造物整个面上产生锈)。
[评价结果]
如表1和图2、4、5所示,在配合了HBP-PGR的实施例1、2的试样液中,冷却时间为1.0秒,可知为与使用比较例4、5的试样液(食盐水)时相同程度的冷却性能。另一方面,配合了PAG的比较例1-比较例3的试样液中,冷却时间为7.8-10.5秒,可知冷却速度慢,冷却性能低。
另外,如表1和图2、5所示,实施例1、2的试样液的冷却时间的差为0.02或0.03秒,可知为与使用比较例4、5的食盐水时相同程度的耐冷却不均性能。另一方面,配合了PAG等的比较例1-比较例3的试样液中,冷却时间的差为0.7-3.0秒,可知容易发生冷却不均。
在实施例1的试样液中,具有实际应用上没有问题的程度的防锈性能,而且添加了水溶性防锈剂的实施例2的试样液中,可知防锈性能进一步提高。即,可知可以自由设定防锈性能。另外,可知实施例1、2的试样液的防锈性能与配合了PAG等的比较例1-比较例3的试样液为相同程度。另一方面可知,添加了水溶性防锈剂的比较例5的食盐水与未添加水溶性防锈剂的比较例4的食盐水相比,其防锈性能几乎没有变化。
由以上结果可以理解,通过使用本发明的水系热处理液组合物进行淬火,可具有高冷却性能、耐冷却不均性能,同时可获得良好的防锈性能。
产业实用性
本发明具有高冷却性能、耐冷却不均性能,同时,可作为防锈性能优异的热处理用的水溶性冷却液使用。
Claims (6)
1.水系热处理液组合物的使用方法,其中,该水系热处理液组合物用于以下任意用途:浸渍淬火、高频淬火,以及固溶化处理时的冷却,其特征在于:该组合物是配合超支化型聚甘油而成的。
2.权利要求1的水系热处理液组合物的使用方法,其特征在于:上述超支化型聚甘油的质均绝对分子量为5,000以上500,000以下。
3.权利要求2的水系热处理液组合物的使用方法,其特征在于:上述超支化型聚甘油的质均绝对分子量为5,000以上100,000以下。
4.权利要求1-3中任一项的水系热处理液组合物的使用方法,其特征在于:以组合物总量为基准,上述超支化型聚甘油的配合量为3%质量以上30%质量以下。
5.权利要求1-3中任一项的水系热处理液组合物的使用方法,其特征在于:该水系热处理液组合物中进一步配合水溶性防锈剂。
6.权利要求4的水系热处理液组合物的使用方法,其特征在于:该水系热处理液组合物中进一步配合水溶性防锈剂。
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JP2617490B2 (ja) * | 1987-10-14 | 1997-06-04 | 出光興産株式会社 | 焼入剤 |
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JP4997581B2 (ja) * | 2001-03-07 | 2012-08-08 | 大同化学工業株式会社 | 水溶性熱処理液 |
DE102006040122B3 (de) * | 2006-08-26 | 2007-10-31 | Degussa Gmbh | Enteisungsmittel und/oder Vereisungsschutzmittel |
US9284625B2 (en) * | 2007-11-20 | 2016-03-15 | Nalco Company | Use of polyols as scale control reagents in the mining processes |
JP2009185179A (ja) * | 2008-02-06 | 2009-08-20 | Nagasaki Univ | 多分岐性高分子及びその製造方法 |
JP5502349B2 (ja) * | 2009-03-13 | 2014-05-28 | 出光興産株式会社 | 水系潤滑剤 |
US8101045B2 (en) * | 2010-01-05 | 2012-01-24 | Nalco Company | Modifying agent for yankee coatings |
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CN101067161A (zh) * | 2007-06-01 | 2007-11-07 | 株洲成华实业有限公司 | 一种水溶性环保淬火介质 |
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CN102753709A (zh) | 2012-10-24 |
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