KR930010532B1 - 냉동기유 - Google Patents

냉동기유 Download PDF

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Publication number
KR930010532B1
KR930010532B1 KR1019880016614A KR880016614A KR930010532B1 KR 930010532 B1 KR930010532 B1 KR 930010532B1 KR 1019880016614 A KR1019880016614 A KR 1019880016614A KR 880016614 A KR880016614 A KR 880016614A KR 930010532 B1 KR930010532 B1 KR 930010532B1
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South Korea
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fluoro
carbon atoms
group
oil
compound represented
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KR1019880016614A
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English (en)
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KR890010171A (ko
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마사또 가네꼬
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이데미쓰 고산 가부시끼가이샤
이데미쓰 쇼스께
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Publication of KR890010171A publication Critical patent/KR890010171A/ko
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Abstract

내용 없음.

Description

냉동기유
본 발명은 냉동기유(냉동기 오일)에 관한 것이며, 더욱 상세하게는 플루오로화합물을 윤활기유에 첨가하기 위해 준비한 특히 플루오로화합물, 플루오로혼합물 또는 조성물을 함유한 각종의 프론화합물(플루오로를 함유한 알칸)과 같은 냉매로 안정하게한 냉동기유에 관한 것이다. 이 냉동기유는 또한, 내소부성 및 기타 성질에 우수한 것이다.
일반적으로 냉동기유에 필요한 성질은 프론을 함유한 냉매로 안정성이 있으며, 또한, 내소부성 및 내마모성과 같은 윤활성에 있어서도 우수하다.
최근에 냉동기는 가혹한 조건하에서 작동하였으며, 더 구체적으로 냉동기의 압축기는 회전수를 증가하였으며, 또한, 인베르티브리화 하였다. 이러한 상황에서 더우기 윤활성에서 향상은 필요 불가피한 조건의 하나가 되게 되었다.
냉동기유의 윤활성(미끄러움)을 향상시키기 위해 트리크레실포스페이트(TCP)와 같은 인화합물 또는 디알킬설피드와 같은 황화합물은 지금까지 기유에 화합하였다. 그러나 이들은 윤활성에서 향상은 한계가 보이며, 또한, 냉매로 안정성이 나쁘다는 문제점을 가지고 있다.
일본 특허 출원 공개 번호 171 487/1983은 트리플루오로클로에틸렌의 저중합체를 공지하였으나, 기유에 대한 용해성이 현저히 나쁘기 때문에 비실용적이다.
본 발명자들은 종래의 냉동기유의 상기에서 언급한 문제점을 극복하기 위해 열심히 연구하였으며, 또한, 높은 내부의 하중 및 각 냉동기에 우수한 안정성을 갖는 냉동기유를 개발해 왔다.
본 발명의 목적은 다양한 프론 화합물과 같은 냉매에 내동기유를 안정하게 제공하는데 있다.
또한, 본 발명의 목적은 각종 냉매와의 상용성에서 우수한 냉동기유를 제공하는데 있다.
본 발명은 다음 일반식
Figure kpo00001
Figure kpo00002
또는,
Figure kpo00003
에 의해 표현된 플루오로 화합물이며, 여기서 R1및 R2중 적어도 하나는 플루오fm를 함유한 기며, 그리고 R3및 R4중에서도 적어도 하나는 플루오로를 함유한 기며, 또한 n은 3-6의 정수고, m도 1-100의 정수이며, 그리고 x 및 y는 다음 표시를 각각 만족한 정수
Figure kpo00004
인 조건하에서 R는 1-30탄소원자를 갖는 알킬기, 6-30탄소원자를 갖는 아릴기 또는 6-30탄소원자를 갖는 사이클로 알킬기며, R1-R8은 1-30탄소원자를 갖는 알킬기, 6-30탄소원자를 갖는 아릴기, 6-30탄소원자를 갖는 사이클로 알킬기, 1-30탄소원자를 갖는 플루오로 치환 알킬기, 1-30탄소원자를 갖는 플루오로 치환 아릴기 또는 6-30탄소원자를 갖는 플루오로 치환 사이클로 알킬기를 자유롭게 가지며, 그리고 R9는 1-30탄소원자를갖는 플루오로 치환 알킬기, 6-30탄소원자를 갖는 플루오로 치환 아릴기, 또는 6-30탄소원자를 갖는 플루오로 치환 사이클로 알킬기를 포함한 냉동기유에 관한 것이다.
본 발명의 냉동기유는 상기의 일반식(I)-(II)에 의해서 표현된 플루오로 화합물을 함유한다. 여기서 일반식(I)에 의해 표현된 플루오로계 화합물은 다양한 종류를 함유한다.
일반식(I)에서 R1및 R2는 상기의 설명한 바와 같으나, 그들중 적어도 하나는 1-30탄소원자를 갖는 플루오로를 함유한 기(1-30탄소원자를 갖는 플루오로 치환 알킬기, 6-30탄소원자를 갖는 플루오로 치환 알릴기, 또한 6-30탄소원자를 갖는 플루오로 치환 사이클로 알킬기)이다.
1-30탄소원자를 갖는 다양한 알킬기중에 바람직한 예는 1-6탄소원자를 갖는 알킬기(메틸기, 에틸기,프로필기, 부틸기등)를 구성한다. 6-30탄소원자를 갖는 아릴기의 바람직한 예는 6-20탄소원자를 갖는 아릴기(페닐기, 토릴기, 크실릴기, 노닐페닐기, 도데실페닐기등)를 함유한다. 6-30탄소원자를 갖는 사이클로 알킬기(사이클로헥실기, 사이클로헵틸기, 메틸사이알킬기의 바람직한 예는 6-30탄소원자를 갖는 사이클로 알킬기(사이클로헥실기, 사이클로헵틸기, 메틸사이클로헥실기, 노닐사이클로헥실기등)를 함유한다. 더우기 1-30탄소원자를 갖는 플루오로 치환 알킬기의 바람직한 예는 1-18탄소원자를 갖는 플루오로 치환 알킬기며, 구체적으로 트리플루오로페닐기, 트리플루오로에틸기, 트리플루오로프로필기, 펜타플루오로프로필기, 트리플루오로부틸기, 트리데카플루오로 옥틸기, 그리고 펜타 에이코사 플루오로 테트라데실기가 있다.
6-30탄소원자를 갖는 플루오로 치환 아릴기의 바람직한 예는 플루오로페닐기, 트리플루오로메틸페닐기, 트리플루오로에틸페닐기, 트리플루오로프로필페닐기, 트리데카플루오로옥틸페닐기 그리고 펜다에이코사플루오로테트라데실 페닐기를 함유한 6-20탄소원자를 갖는 플루오로 치환 아릴기가 있다. 6-30탄소원자를 갖는 플루오로 치환 사이클로알킬기는 플루오로사이클로헥실기, 트리플루오로플로필사이클로헥실기, 트리플루오로에틸사이클로헥실기, 트리플루오로메틸사이클로헥실기, 트리데카플루오로사이클로헥실기, 그리고 펜타에 이코사플루오로테트라데실사이클로헥실기를 함유한 6-20탄소원자를 갖는 플루오로 치환 사이클로알킬기가 바람직하다. n은 3-6의 정수다.
일반식(I)에 의해 표현된 플루오로 화합물의 전형적인 예는 1,3,5-트리(3,3,3 -트리플루오로프로필)-1,3,5-트리메틸사이클로트리실록산; 1,3,5-트리(3,3,3-트리플루오로프로필)-1,3,5-트리이소도데실사이클로트리실록산, 1,1,3,3,5,5-헥사(3 ,3,3-트리플루오로프로필)사이클로트리실록산이다.
일반식(II)에 의해 표현된 플루오로 화합물은 여러종류를 함유한다. 상기식(II)에서 R3-R8은 상기에서 규정한 바와 같다.
m이 둘이상일때, R5및 R6의 각각은 동일하거나 다를 수가 있다.
그러나 R3-R8중 적어도 하나는 플루오로를 함유한 기이다.
일반식(II)에서 m은 1-100(바람직하게는 2-50)의 정수다. 그러나 일반적으로 R3및 R8중의 플루오로 함량 치환기는 m이 크게 된 것처럼 큰 것이 바람직하다. 일반식(II)에 의해 표현된 플루오로 화합물의 전형적인 예는 일반식(II')에 의해 표현된 폴리플루오로 알킬실록산이다.
Figure kpo00005
상기의 화합물의 시판된 제품으로 상기의 식(II')에 의해 표현된 폴리플루오로알킬실록산(m은 약 10-30이고, 상품명 : FL-100, 시네쯔실리콘사 제품)을 적용할 수 있다.
m이 2일때, 일반식(II)에 의해 표현된 플루오르 화합물의 예는 일반식(II'')에 의해 표현된 플루오로 화합물이다.
Figure kpo00006
일반식(II'')에서 R3-R8은 상기의 규정한 바와 같으며, 그리고 그들중의 적어도 하나는 플루오로를 함유한 기이다. 그들중의 R3및 R4는 플루오로를 함유한 기(1-30탄소원자를 알킬기, 6-30탄소원자를 갖는 아릴기 또는 6-30탄소원자를 갖는 사이클로알킬기를 포함)가 없는 것이 바람직하다. 이 일반식(II'')에 의해 표현된 플루오로를 함유한 화합물의 예를 들면은 3-(3,3,3,-트리플루오로프로필)-1,1,1,3,5,5,5-헵타메틸트리실록산 및 3,3-디(3,3,3-트리플루오로프로필(-1,1,1,5,5,5-헥사메틸트리실록산이 있다.
더우기, 일반식(Ⅲ)에 의해 표현된 플루오로 화합물은 X 및 Y의 수에 따라 변한다. 예를 들면 X=1, 그리고 Y=1일때, 일반식(Ⅲ)은 다음의 식에 의해 표현된 플루오로 화합물을 나타낸다.
Figure kpo00007
(여기서 R 및 R9는 상기의 규정한 바와 같다. 그러나 3RS는 동일하거나 다르다. ) 그리고 X=1,그리고 Y=0일때는 일반식 (Ⅲ)가 다음식에 의해 표현된 플루오로 화합물을 나타낸다.
Figure kpo00008
(여기서 R 및 R9는 상기의 규정한 바와 같다. 그러나 3RS는 동일하거나 다르다. ) 여기서 R9는 상기에서 설명한 바와 같이 플루오로를 함유한 기(1-30탄소원자를 갖는 플루오로 치환 알킬기, 6-30탄소원자를 갖는 플루오로 치환 알킬기 또는 6-30탄소원자를 갖는 플루오로 치환 사이클로 알킬기)며, 그리고 더 상세하게는 상기의 설명한 R1및 R2에 의해서 나타난 기와 동일하다.
일반식(Ⅲ)에 의해 표현된 플루오로 화합물의 예를 들면은 3, 3, 3-트리플루오로프로필-트리메독시실란, 3, 3, 3-트리플루오로프로필-트리데카옥시실산, 그리고 디메독시메틸-3, 3, 3-트리플루오로프로필실란이 있다.
본 발명의 냉동기유는 일반식(I)-(Ⅲ)에 의해 표현된 플루오로 화합물중 적어도 한종류를 함유하며, 그리고 냉동기유에서 그 내용물은 제한이 없다.
본 발명의 냉동기유는 상기한 일반식(I)-(Ⅲ)에 의해 표현된 플루오로 화합물을 홀로 구성하며, 또한 주성분으로 상기 플루오로 화합물을 함유하며, 더우기 이것은 소량으로 성분을 첨가한 상기의 플루오로 화합물을 함유한다.
보통 냉동기유에서 상기의 일반식(I)-(Ⅲ)에 의해 표현된 플루오로 화합물의 비율은 적어도 0,0005중량% 이어야 하며, 그리고 목적에 따라서는 0,0005-100중 량% 범위로부터 적당하게 선택할 수 있다.
그러나 비율이 냉동기유를 위해 기유의 100중량부에서 용해성 또는 경제적 효용성의 관점으로부터 0.005-10중량부의 범위로 고정한 것이 바람직하다. 플루오로 화합물량을 너무 적게 첨가하면 목적과 효과를 충분히 나타낼 수 없다.
본 발명의 냉동기유에서 광유, 함성유를 단독으로 또는 이 두 화합물을 기유로 사용할 수 있다. 상기 기유의 성질은 한정이 없지만 보통 4℃에서 동점도가 5-1000cst이며, 바람직하게는 7-500cst며, 그리고 더욱 바람직하게는 10-300cst이다. 여기서 동점도가 5cst이하일때, 증발에 의해 기름 소비량이 크고 기름 순환량이 증가하며, 그리고 시일링성은 나쁘다는 문제점이 발생한다.
기유로 여기에 사용한 광유의 전형적인 예는 파라핀계 원유, 중간계 원유 또는 나프텐계 원유를 상압 중류 또는 상압증류로부터 잔류유를 감압증류하여 얻은 증류유이며, 상기의 보통 방법에 따라서 정제하여 얻은 정제유 예를 들면 용제정제유, 수소첨가한 정제유, 탈왁스처리유 그리고 백토처리유등이 있다.
합성유의 대표적인 예를 들면은 알킬벤젠, 알킬디페닐, 폴리-α-올레핀 에스테르(힌더에스테르, 2염기산 에스테르, 폴리올에스테르, 인산에스테르)폴리에스테르(폴리페닐에테르, 폴리글리콜에테르) 그리고 실리콘 오일등이 있다.
본 발명의 냉동기유의 기유로서 상기 언급한 광유 또는 합성유를 사용할 수 있다. 난용성 냉매에 대하여 용해성 또는 안정성을 고려하였으나, 합성유가 바람직하며, 그리고 더욱 바람직하게는 알킬벤젠, 알킬디페닐, 에스테르 그리고 폴리에테르가 있다.
본 발명의 냉동기유에서 필요한 경우에 트리크레실포스페이트(TCP)를 함유한 마모 방지제, 페닐글리시딜에테르(PGE)를 함유한 염소 보착제, 알파-나프틸아민, 2,6-디-테르트-부틸-P-크레졸(DBPC)와 같은 산화 방지제, 벤조 트리아졸을 함유한 금속 불활성화제, 그리고 실리콘 오일을 함유한 소포제등을 적당량 배합한 것이 효과적이다.
상기에서 설명한 바와 같이 본 발명의 냉동기유는 다양한 냉매로 예를 들면, 프론-22(모노클로로디플루오로메탄), 프론-23(트리프로오로메탄), 프론-123(1,1-디클로로-2,2,2-트리플루오로메탄), 프론-134a(1,1,1,2-테트라 플루오로에탄), 프론-134(1,1,2,2-테트라플루오로에탄) 그리고 프론-152a(1,1-디플루오로에탄)등에 안정하며, 그리고 보통 난용성 냉매에 관하여 냉매로 상용성 및 안정성이 우수한다.
더우기 본 발명의 냉동기유는 내소부성 및 내마모성이 높으며, 증류에 의한 기름 소비량이 줄어들고 또한 기름 순환량이 줄어든다.
따라서, 본 발명의 냉동기유는 냉매로 다양한 프론 화합물을 사용한 냉동기, 쿨러(특히, 자동차 에어콘)그리고 히이터 펌프를 윤활제로 효과적으로 사용한다.
본 발명은 다음 실시예와 비교예에서 보다 상세하게 설명한다.
다음의 실시예 및 비교예에서 평가는 다음의 방법으로 하여 실시한다.
열 안정성 시험(시엘드 튜브시험)
시료와 프론 -22와의 2 : 1(중량) 혼합물을 철, 구리, 알루미늄의 촉매와 함께 유리관에 넣고, 동봉하여 175℃에서 720시간동안 가열한 후, 석출물의 외관, 구조를 시험한다.
소부시험(파렉스 소부시험)
ASTM D 3233에 따라 소부하중(파운드)는 프론-22의 불어넣는 양을 10l/hour의 조건하에서 결정한다.
마모시험(파렉스 마모시험)
프론-22의 불어넣는 양 101/hour 하중 : 300파운드, 시간 : 2시간의 조건하에서 마찰량을 측정한다.
상용성(2층 분리온도)
시료와 프론-22은 2 : 8(중량) 비율로 혼합하고, 그리고 혼합이 2층으로 분리한 온도를 측정한다. X는 20℃이상의 2층 분리온도를 나타내며, 또한 O은 20℃이상의 온도에서 관찰할 수 없는 분리를 나타낸다.
[실시예 1-10 및 비교예 1-6]
조성물은 기유로 표 1에서 광유, 폴리-α-올레핀, 알킬벤젼, 힌더에스테르 또는 폴리글리콜과 플루오로화합물로서 일반식 (I')의 플루오로 실리콘을 적용(식에서 m은 약 12(평균)이고, 40℃에서 동점도 : 80cst, 점도지수 : 210)하여 제조하며 그리고 상기의 방법에 따라 성능을 평가한다.
결과는 표 1및 3에 나타나 있다.
[실시예 11-27 및 비교예 7-10]
냉동기유는 상기의 설명한 양에서 표 4에 나타난 광유, 알킬벤젼, 폴리글리콜 그리고 플루오로 화합물을 배합하여 제조하고 그리고 상기의 방법에 따라서 성능을 평가한다. 결과는 표 4에 나타나 있다.
[표 1]
Figure kpo00009
[표 2]
Figure kpo00010
* 플루오로화 실리콘 대신에 트리크레실포스페이트(TCP)를 첨가한다.
** 일반식(I')에서 m이 약 27(평균)을 갖는 플루오로화 실리콘이며, 40℃에서 동점도가 210cst며, 그리고 점도지수는 220을 사용한다.
[표 3]
Figure kpo00011
* 플루오로화 실리콘 대신에 트리크레실포스페이트(TCP)를 첨가한다.
** 일반식(I')에서 m이 약 27(평균)을 갖는 플루오로화 실리콘이며, 40℃에서 동점도가 210cst며, 그리고 점도지수는 220을 사용한다.
[표 4]
Figure kpo00012
A : 1, 3, 5-트리(3, 3, 3-트리플루오로프로필-1, 3, 5-트리메틸사이클로실록산
B : 3-3,3,3-트리플루오로프로필)-1,1,1,3,5,5,5-헵타메틸트리실록산
C : 디메톡시메틸-3,3,3-트리플루오로프로필실란
E : 파라핀계 광유 40℃에서 동점도 : 56cst, 황성분 : 0.01중량%이하
F : 알킬벤젼, 40℃에서 동점도 : 32cst
G : 폴리글리콜, 40℃에서 동점도 : 24cst

Claims (9)

  1. 다음 일반식
    Figure kpo00013
    Figure kpo00014
    또는
    Figure kpo00015
    에 의해 표현된 플루오로 화합물이며, 여기서 R1및 R8중 적어도 하나는 플루오로르 함유한 기며, 그리고 중에서도 적어도 하나는 플루오로를 함유한 기며, 또한 n은 3-6의 정수고, m도 1-100의 정수이며, 그리고 X 및 Y는 다음 표시를 각각 만족한 정수
    Figure kpo00016
    인 조건하에서 R는 1-30탄소원자를 갖는 알킬기, 6-30탄소원자를 갖는 아릴기 또는 6-30탄소원자를 갖는 사이클로 알킬기며, R1-R8은 1-30탄소원자를 갖는 알킬기, 6-30탄소원자를 갖는 아릴기, 6-30탄소원자를 갖는 사이클로알킬기, 1-30탄소원자를 갖는 플루오로 치환 알킬기, 1-30탄소원자를 갖는 플루오로 치환 아릴기 또는 6-30탄소원자를 갖는 플루오로 치환 사이클로 알킬기를 자유롭게 가지며, 그리고 R9는 1-30탄소원자를 갖는 플루오로 치환 알킬기, 6-30탄소원자를 갖는 플루오로 치환 아릴기, 또는 6-30 탄소원자를 갖는 플루오로 치환 사이클로 알킬기를 포함한 냉동기유.
  2. 제1항에 있어서, 일반식(I)에 의해 표현된 플루오로 화합물은 1,3,5-트리(3, 3,3 -트리플루오로프로필)-1,3,5-트리메틸-사이클로트리실록산; 1,3,5-트리(3,3, 3-트리플루오로프로필)-1,3,5-트리이소도데실사이클로트리실록산 그리고 1,1,3,3, 5,5-헥사(3,3,3-트리플루오로프로필) 사이클로트리실록산을 함유한 기로부터 선택한 적어도 한종의 화합물을 갖는 냉동기유.
  3. 제1항에 있어서, 일반식(II')에 의해 표현된 플루오로 화합물은 다음 일반식(II')
    Figure kpo00017
    (여기서 m은 상기와 같다.)
    에 의해 표현된 적어도 한종 화합물을 갖는 냉동기유.
  4. 제1항에 있어서, 일반식(II')에 의해 표현된 플루오로 화합물은 다음 일반식(II')
    Figure kpo00018
    (여기서 R3-R8는 상기와 같다.)
    에 의해 표현된 적어도 한종 화합물을 갖는 냉동기유.
  5. 제4항에 있어서, 일반식(II'')에 의해 표현된 플루오로 화합물은 3-(3,3,3-트리플루오로프로필)-1,1,1,3,5,5,5-헵타메틸-트리실록산 및 3,3-디(3,3,3-트리플루오로프로필)-1,1,1,5,5,5-헥사메틸트리실록산을 함유한 기로부터 선택한 적어도 한종 화합물을 갖는 냉동기유.
  6. 제1항에 있어서, 일반식(Ⅲ)에 의해 표현된 플루오로 화합물은 3,3,3-트리플루오로프로필트리메톡시실란, 3,3,3-트리플루오로프로필트리데카옥시실란 그리고 디메톡시메틸-3,3,3-트리플루오로프로필실란을 함유한 기로부터 선택한 적어도 한종 화합물을 갖는 냉동기유.
  7. 제1항에 있어서, 주요성분으로 규정된 플루오로 화합물을 함유한 냉동기유.
  8. 제1항에 있어서, 기유 100중량부와 약 0.005-10중량부를 함유한 냉동기유.
  9. 제8항에 있어서, 기유는 40℃에서 동점도가 100cst를 갖는 광유, 합성유 또는 그 혼합물을 함유한 냉동기유.
KR1019880016614A 1987-12-11 1988-12-12 냉동기유 KR930010532B1 (ko)

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