Jump to content

Rorschach

网站版主
 查看个人资料  查看TA的活动

  • 帖子总数

    19,849

  • 注册时间

  • 上次访问

 Content Type 

博客条文 由 Rorschach 发布的

  1. Rorschach
    今天您喝水了吗？？

    我已经喝了6年的桶装水了

    不得不喝

    看完这些图片之后

    相信您也会喝桶装水的……


    点击小图察看大图


    喝吧喝吧不是罪




    铁？？地球在流血！！




    泡沫丰富的啤酒才是好啤酒……
  2. Rorschach

    今天被骂了

    By Rorschach,

    为了骂我

    还专门申请了一个ID

    真难得

    太荣幸了

    难得有人这么关注我

    很久没听到**这个词了



    没办法

    也没露个真脸

    拿这种人没办法

    找也找不到他真人

    只能让他过过嘴瘾

    不知道现实生活中是什么样子的
  4. Rorschach
    有录音。。。。

    这倒无所谓。。。

    录音吧

    有回音

    我一边说一边听自己说。。。

    支支吾吾半天都没说清楚。。。

    结果给我打了4次电话都没找到地方

    值班的太2了

    今天从高架桥上虚虚来着

    浇到了桥下的2只汪汪

    一只黄的一只黑的

    黑的貌似很享受的样子

    黄的还知道抬头看。。。。。

    估计看到我的小JJ了
  5. Rorschach
    牢记历史勿忘国耻

    　　3月15日，记者得知金山公司准备在天津连邦举行国内第一部反映
    抗日战争题材的大型游戏——《抗日之地雷战》的发行纪念活动，同时
    金山公司总裁求伯君还将在南开大学举行讲座，于是匆匆赶往天津进行
    实地采访。
    　　中午11点30分，我们来到天津连邦专卖店，店外挂着两条醒目的大
    横幅，很多人纷纷询问什么时候可以签名，天津连邦专卖店的负责人只
    好在店外贴出安民告示：签名时间12：30～3：30。
    　　12：00，有人说求伯君在南开大学，于是一大群记者又驱车前往。
    为了避免记者们的“围攻”，求伯君临时在南开大学找到一间会议室，
    回答了记者的问题。
    　　有记者问，据说昨天你们已在南京大屠杀纪念馆举行了首发式，为
    什么今天在天津举办？求伯君回答说，为警醒人们“牢记历史，勿忘国
    耻”，我们与江苏省出版总社、南京大屠杀纪念馆一起在南京大屠杀纪
    念馆共同举办了大型的发布会，其意不言自明。今天在天津举行首发式
    同样有特别的意义。两年前，11名热血青年在这里抵制加工日本文化侵
    略软件《提督的决断》，因为他们的义举，才促使我们更快地开发出《
    抗日之地雷战》这部爱国题材的大型游戏。
    　　北京金山软件公司的总经理雷军补充说，我们开发的这部游戏，并
    不指望赚钱，只希望能给我们的下一代提供一部很好的爱国主义教材，
    让我们的下一代牢记这一段历史。
    　　会上，记者见到了抵制《提督的决断》的4位天津热血青年：梁广
    明、郭海京、祁魏和高原。他们讲述了两年前抵制加工《提督的决断》
    的简单过程。1996年6月，日本光荣公司天津公司欲在天津加工游戏《
    提督的决断》，该游戏软件以二战时太平洋战争为时代背景，但这部由
    日本人开发的游戏严重歪曲历史，美化日本侵略者，严重伤害了中国人
    民的感情。为此，天津公司电脑动画部的4位中国职员向日方提出了严正
    抗议，但日方对此反映冷淡。1996年7月5日，天津市新闻出版局对天津
    光荣公司进行检查，经查，该公司未经批准，擅自加工生产带有美化法
    西斯内容、损害中国人民感情的二战题材游戏软件。为此，执法部门对
    天津光荣公司作出了勒令停业审查处理。同年10月7日，这4位热血青年
    集体提出辞职，10月9日，另外7名职员也联名辞职，以支持4青年的爱国
    行动。此后，北京，上海等地全力查禁《提督的决断》，中央电视台《
    焦点访谈》对此作了专门报道。
    　　雷军告诉我们，当这11位青年离职后，还无去向时，在珠海的求伯
    君先生专程北上，力邀11位青年南下，共同研制开发表现民族气节的系
    列软件。经过一年多的时间，《抗日之地雷战》终于问世。因天津热血
    青年的义举而引发的中国游戏软件的革命，经过近两年的努力终于有了
    良好开端。（编者按：在这11名热血热青年中，有6名青年目前已在前导
    公司开发游戏软件，其中包括梁广明、郭海京、祁魏、高原。）
    　　求伯君最后谈到，我国的游戏软件目前存在着一些误区，游戏内容
    不是武侠打斗就是妖魔鬼怪，虽然也出了几款古典名著的游戏，但离现
    实过于遥远。天津热血青年的壮举，则不仅维护了民族的尊严，也给民
    族软件业以启迪，拓展了国产游戏软件的题材范围。事实上，爱国主义
    题材的游戏软件不仅可以拉近游戏者的现实感，更重要的是，能增强民
    族自豪感和民族凝聚力，寓教育于娱乐之中，起到潜移默化的作用。
    　　当我们与求伯君一起赶到天津连邦专卖店时已是下午2:30，只见专
    卖店已被人围得严严实实。很多买了《抗日之地雷战》的用户已在此等
    候了很久。记者好不容易才挤进去，见许多人围着求伯君纷纷要求签名
    留念，场面热烈感人。一位正在接受天津电视台采访的用户说，我早就
    想买这种爱国题材的游戏给孩子，让他们记住这段历史。我很感谢金山
    公司开发出这种反映抗日战争题材的电脑游戏，希望以后有更多的爱国
    题材游戏上市。
    　　求伯君由于连续几天劳累过度，右眼血管渗血，但他仍坚持到下午
    4:00才去医院检查。
    　　晚上8:00，在南开大学一个大厅里，求伯君向数百名大学生作了一
    场精彩的技术报告，主要内容包括：WPS十年开发历史，金山公司正在做
    什么，国内软件业面临的问题等。在场学生对求伯君的演讲不时报以热
    烈的掌声。大学生们表示，要支持民族软件产业，支持正版软件。演讲
    结束后，大学生们久久不愿离去，纷纷上台请求伯君签名留念。


    转子：北大未名
  6. Rorschach

    Tell Me

    By Rorschach,

    너도 날 좋아할 줄은 몰랐어
    어쩌면 좋아 너무나 좋아
    꿈만 같아서 나 내자신을 자꾸
    꼬집어봐 너무나 좋아
    네가 날 혹시 안 좋아할까봐
    혼자 얼마나 애태운지 몰라
    그런데 너도 날 사랑한다니
    어머나 다시 한 번 말해봐

    **Tell me, tell me, tell tell tell tell tell tell me
    나를 사랑한다고 날 기다려왔다고
    tell me, tell me, tell tell tell tell tell tell me
    내가 필요하다 말해 말해줘요
    tell me, tell me, tell tell tell tell tell tell me
    자꾸만 듣고 싶어 계속 내게 말해줘
    tell me, tell me, tell tell tell tell tell tell me
    꿈이 아니라고 말해 말해줘요

    어쩜 내 가슴이 이렇게 뛰니
    가슴이 정말 터질 것 같아
    네가 날 볼 때면 전기에 감전된
    사람처럼 전기가 올라
    얼마나 오래 기다린지 몰라
    얼마나 오래 꿈꿨는지 몰라
    그런데 네가 날 사랑한다니
    어머나 다시 한 번 말해봐

    Bridge tell me, tell me, tell me you want me,
    want me, wante too
    Tell me, tell me, tell me
    you love me too, love me too

    얼마나 오래 기다린지 몰라
    얼마나 오래 꿈꿨는지 몰라
    그런데 네가 날 사랑한다니
    어머나 다시 한 번 말해봐
  7. Rorschach
    首先说明一下

    外国论坛转来的

    不知道管用否

    可能有些人已经知道了就是不说

    BS一下

    不过我放上来这些人也会BS我。。。。。。。。。

    爱咋咋地吧

    管用的话您顶一下帖子

    不管用的话骂两句也无妨

    我懒的试……

    反正我的fps比较稳定

    寻找小白鼠~~~~

    r_drawSun "0"
    r_drawDecals "0"
    r_rendererPreference "0"
    r_aaAlpha "0"
    r_detail "0"
    r_picmip "3"
    r_picmip_manual "1"
    r_picmip_bump "3"
    r_picmip_spec "3"
    r_distortion "0"
    r_dlightlimit "0"
    r_fastskin "1"
    r_ingamevideo "0"
    r_mutliGPU "1"
    r_outdoor "1"
    r_texFilterAnisoMax "1"
    r_texFilterMipMode "3"
    r_zFeather "0"
    cg_brass "0"
    cg_blood "0"
    cg_marks_ents_player_only "1"
    fx_marks "0"
    fx_marks_ents "0"
    fx_marks_smodels "0"
    sm_enable "0"
    cg_fov "80"
    com_maxfps "100"
    cl_maxpackets "100"
    snaps "30"
    rate "25000"

    修改方法

    F:\Program Files\Activision\Call of Duty 4 - Modern Warfare\players\profiles\911pm

    找

    config_mp.cfg

    修改里面的东西

    不一定是911pm

    注意备份原文件

    那个文件可以用.txt打开
  9. Rorschach

    关于油炸

    By Rorschach,

    炸的东西一定要在油冷前捞出

    要么会吸很多油的

    还有就是软炸椒盐的问题

    市场上目前能买到的基本上都有味精

    目前我还不知道味精遇高热会咋样

    所以建议买来材料自己做

    我个人的配料是

    花椒：麻椒：芝麻：盐=3：1：4：1

    或者干脆不放盐

    花椒

    麻椒

    芝麻

    这三种都要干锅炒香

    放在捣蒜罐里

    捣碎混合

    找个干净罐子放起来

    吃什么东西都能加

    甚至是喝大米稀饭时候……
  10. Rorschach
    上面这张是尼康CoolPix忘了多少……照的

    tif格式

    下面这张是佳能Q117照的

    底片直接扫描仪扫描……



    直接扫描底片效果还是不是很好

    上面的白点竟然是药渣

    北辰区津北照相馆实在是不负责任

    白条是我家灰尘

    等照片出来再扫

    就是不一样效果了

    毕竟Q117被称为穷人的莱卡
  11. Rorschach

    今天情人节

    By Rorschach,

    在车站看到一个男生

    左手抱着一个好大抱抱熊……

    至少有一米二高

    右手在狂按手机

    脸上在狂流眼泪……

    我也在狂流

    口水……

    问见烧烤摊的香味了……
  12. Rorschach
    今天下好了Combat Mission 3 Afrika Korps

    安装之后发现黑屏

    而且异常上当

    这个不是Afrika Korps

    而是Combat Mission 3 Afrika Korps



    俺的配置

    显卡7600

    2G内存

    奔4=3.2

    标准XP系统

    800*600/85hz

    95年IBM键盘/罗技m-s61

    下载光盘景象后虚拟光驱安装

    运行游戏时发现黑屏



    解决方法是把分辨率设置成1024*760

    出现德文提示

    点上面那个

    即可运行游戏
  14. Rorschach

    开始砸核桃

    By Rorschach,

    两大袋子核桃

    据说吃核桃可以补脑子

    感觉也锻炼身体

    最近在捉摸电池的问题

    做一个备用电源



    可以接在相机上用的

    本身是一个坏的笔记本的电池



    还是老款相机的镜头大
  15. Rorschach

    薄荷种子这两天发出去

    By Rorschach,

    还在开花

    开了都快3个月了

    终于找到种子了

    比花还小……

    花比小米粒还小

    小米粒比大米粒还小

    ………………………………

    ………………

    总之就是很小很小

    这两天寄出去
  16. Rorschach
    貌似以前都是我在帮她照顾她

    今日遇险情

    还得Lp相助



    今日独自外出游玩

    突然发现身上的钱花光了……

    身无分文

    在离家20Km的荒芜地带

    简单的说就是回不去了



    打了个电话给Lp

    不到2个小时就来了

    还带来了急需的水源



    来的真及时……




    近日荔枝吃多了

    满嘴大燎泡

    痛苦难耐

    提醒大家注意饮食和理性
  17. Rorschach

    二战德军步兵战术手势

    By Rorschach,

    Schutzenreihe: The single file advance is usually the most practical way to cross difficult terrain. Some control is lost with troops in the rear. The first contact is likely to be at the front of the column.




    The Squad Leader's hand signal is the arm waved back and forth in an exaggerated manner.


    =========================================================


    Doppelreihe: A parallel march used mainly to move along roads, but also employed to reduce casualties from mortars. Also allows motor vehicles to pass. Even numbers to the left, odd to the right.





    The Squad Leader's hand signal is the double-arm fanning motion, forward and back.


    ==========================================================


    Kampflinie: This skirmish line is usually used for mopping up operations, the last stages of an assault or to search an area. Its's strongpoint is strong firepower at the front but it lacks control factors.





    The Squad Leader's hand signal is the outstretched arms.


    =========================================================


    "T": the "T" is used to allow the formation to move with firepower to the front and yet be able to respond to enemy fire from unexpected directions.





    The Squad Leader's hand signal is the upright arm waved side to side


    =========================================================


    "V": 'The "V" is used much in the same way as the "T" formation, except there is more firepower available at the front.





    The Squad Leader's hand signal is both arms bent downward in an inverted "V" and waved in line with the body.







  19. Rorschach

    天津的解放桥

    By Rorschach,

    解放桥原名叫万国桥。因为此桥由当时的法租界工部局主持修建，并坐落于法租界入口处，也叫“法国桥”。
    由法国的达德与施奈尔公司设计、建造，这座桥前前后后建了三年。





    前些日子翻修过



    为了能通过重型货轮

    桥设计的可以向两侧开启





    新修的乔

    忘了交涉呢没名字了……



  20. Rorschach

    玩了下Pi Story

    By Rorschach,

    首先鸣谢=HK-Kr'z=K_Z同学帮5申请的帐号

    先把图发出来

    很像彩虹岛





    目前注册还是封锁大陆的IP段

    估计能玩上过一段时间也会被封号

    发现美服的好处就是没有防沉迷系统。。。。。

    全英文的

    玩着还是有点吃力

    10级转职


























  24. Rorschach
    United States Patent [i91 US005 166297A [iI] Patent Number: 5,166,297 O'Lenick, Jr. 1451 Date of Patent: Nov. 24, 1992 [54] SILICONE ESTER QUATERNARY cone copolyol halo ester intermediate which conforms COMPOUNDS to the following structure; [75] Inventor: Anthony J. O'Lenick, Jr., Lilburn, Ga. R"O-(CH2CH20),--(CH2CH(CH3)0)y-(CH2CH20),--(CH2)3 [73] Assignee: Siltech Inc., Norcross, Ga. [21] Appl. NO.: 822,752 0- Si [22] Filed: Jan. 21, 1992 CH3 Related U.S. Application Data [63] Continuation-in-part of Ser. No. 674,410, Mar. 25, 1991, Pat. No. 5,098,979. [5 11 Int. C1.5 .............................................C. 08G 77/06 U.S. C1. ........................................ 528/26; 528/15; 528/3 1; 525/474 Field of Search ....................... 528/26, 15, 31, 28; 427/387;424/70; 548/951 References Cited wherein R" is -C(O)-CH2-Cl; a is an integer from 0 to 200; b is an integer from 0 to 200; c is an integer from 1 to 200: U.S. PATENT DOCUMENTS R1 is selected from -(cH~),cH~ or phenyl; 4,185,087 1/1980 Morlino et al. ....................... 424/70 n is an integer from 0 to 10; 4,800,077 1/1989 O'Lenick, Jr. et al. .............. 424/70 R2 is -(CH2)3-(0CH2CH2)x-(0CH2CH(CH3- 5,070,168 12/1991 O'Lenick, Jr. ........................ 528/10 ))y-(OCH2CH2)z-OH; 5,073,619 12/1991 O'Lenick, Jr. ........................ 528/26 x, y and z are integers and are independently selected 5,098,979 3/1992 O'Lenick, Jr. ........................ 528/15 from 0 to 20, which is useful as an intermediate for Primary Examiner-John C. Bleutge reaction with amines to prepare silicone based qua- Assistant Examiner-M. W. Glass ternary compounds. The present invention is directed to a novel dimethi- 8 Claims, No Drawings SILICONE ESTER QUATERNARY COMPOUNDS RELATED APPLICATION This application is a continuation in part of copending 5 application Ser. No. 07/674,410, filed Mar. 25, 1991, now U.S. Pat. No. 5,098,979. BACKGROUND OF THE INVENTION (1) Field of Invention 10 The present invention relates to a series of novel cpaternHry silicone polymers, an intermediate useful in softening hair, and fiber and conditioning skin. Since the compounds of the present invention are high molecular weight silicone polymers, they have a high degree of oxidative stability, even at elevated temperatures. In addition, these compounds are non volatile and unlike many other traditional fatty quaternary compounds are non yellowing when applied to textile sub- 20 strates and are non irritating to eyes and skin. The compounds of the present invention are prepared by the reaction of chloracetic acid with a pendant hydroxyl group which is present on a silicone polymer, followed by the reaction of the halo-ester with a tertiary 25 amine to give a quaternary compound. In a preferred embodiment the hydroxy containing silicone polymer has been alkoxylated with ethylene oxide, propylene ,297 2 This is achieved by selection of the hydroxy silicone polymer used as a raw material. Application of the compounds of the invention can be from solvent, aqueous dispersion or solution, or applied neat in these process. It is anticipated that the effective conditioning concentration of the compound of this invention ranges from 0.1% to 25% by weight. The silicone polymers, suitable as raw materials, in a preferred embodiment, contain varying amounts of ethylene oxide, propylene oxide or mixtures thereof. The presence of the oxide in the silicone polymer results in compounds with an inverse cloud point. Inverse cloud point phenomenon are well known to those skilled in the art of nonionic surface active agents. The inverse cloud point is defined as a temperature above which the polymer has minimal solubility in water. If heat is applied to an aqueous solution of the nonionic at the inverse cloud point the material will become insoluble, and the solution will turn milky. It is at this point that the polymer has minimal water solubility. Since the product is no longer in solution at above this temperature, it is within this temperature range that the product has maximum substantivity to a fiber. The ability to use temperature to deposit a lubricant, antistat onto a fiber offers a great advantage in cost effectiveness of fiber treatment, and results in less product usage. (3) DESCRIPTION OF THE - - - ARTS AND oxide, or mixtuies thereof. ~he-abilityto regulate both PRACTICES the type of alk~leneo xide and amount of alk~leneo xide 30 Silicone oils (dimethylpolysiloxane) have been present in the silicone polymer results in a series of lcnown to be active at the surface of plastic, cellulosic products ranging in water/oil solubility. The technol- ,d synthetic fibers as well as paper. it^ the fact Ogy used produce the the present that they are lubricants that are stable to oxidation, their invention is very flexible and allows us to prepare per- high cost and lack of durability has made them cost formance tailored molecules for specific applications. 35 prohibitive in most application areas. silicone oils need (2) Object of the Invention to be emulsified prior to application. This requires high pressure equipment, surface active agents and generally It is the object of the present invention to provide a in a milky emulsion, ~ ~have expe~rienct.d l ~ i series of novel quaternary silicone polymers, which are stability problems both in terns of freeze thaw instabilsubstantive to skin and hair. This substantivity results in 4 ity and upon heating. This has resulted in minimal acsuperior softening, conditioning and antistatic proper- ceptance of them in commercial products. ties. The compounds of the present invention contain a The low eficiency of silicone oils is due to the fact fatty portion which is derived from a fatty amine. Incor- that the oil is very water insoluble. Emulsions are generporation of this type of group into the silicone molecule ally which contain silicone dispersed in miresults in increased solubility in many organic solvents. 45 celles. While this method of application is easier for This ability to marry fatty chemistry with silicone processing, much of the oil stays in the surfactant michemistry results in unexpected solubilities and surface celle and never gets deposited on the fiber. That which active properties. The compounds also contain varying does deposit on the fiber surface remains there by hy- - amounts of ethylene oxide and propylene oxide in the drophobic binding, not ionic bonding. Since the polydimolecule. This results in the ability to vary water soh- 50 methylsiloxane is not ionically bonded the effect is very bility and introduce an inverse cloud point into the transient. The product is removed with one washing. molecule. Inverse cloud point is well known to those Fatty quaternary compounds have been known as skilled in the surfactant art. It is generally found in softerners for many years. They have a much lower nonionic surface active agents. It is not found in quater- molecular weight than the silicone based compounds of nary compounds. The inverse cloud point is that tem- 55 the present invention. For this reason, they are much perature at which a soluble compound looses it's solu- more irritating to skin and eyes than those materials bility in water. Inverse cloud point, also called high based upon silicone polymers. cloud point, is thought to be associated with the ability Standard fatty quaternary compounds are prepared of the alkyleneoxide chain to hydrogen bond with the by quaternization of a tertiary amine with such agents as water. 60 benzyl chloride or di-methyl sulfate or di-ethyl sulfate It is another objective of the current invention to or methyl cloride. These materials are relatively inexprovide quaternary silicone polymers which have very pensive but offer several key disadvantages. These inlow irritation values when applied to skin and eyes. clude yellowing of fabrics, a tendency to build-up upon Irritation is a major problem with traditional fatty cati- repeated treatment, and variability in hand (i.e. softness onic materials. 65 and feel). Standard softeners used are selected from the Still another object of the present invention is to following classes: provide a series of quaternary silicone polymers which Class #I. Alkyl Imidazoline Quaternary Compounds have differing solubilities in water and organic solvents. made from the quaternization of an imidazoline made 5,166: 3 by reacting diethylenetriamine, and a high molecular weight fatty acid such as stearic acid. The standard quaternizating agents are di-ethyl sulfate, or methyl chloride, or di-methyl sulfate, or methyl chloride or benzyl chloride. 5 Class #2. Alkyl or dialkyl tertiary amines quaternized with benzyl chloride or di-ethyl sulfate or methyl chloride or di-methyl sulfate. Class #3. Quaternary compounds of ethoxylated, propoxylated or nonalkoxylated amido amines derived 10 from the reaction of a high molecular weight fatty acid like stearic acid and a polyamine like diethylene triamine. The standard quaternizating agents are di-ethyl sulfate or di-methyl sulfate or methyl chloride or benzyl THE INVENTION 1) Summary of the Invention The present invention relates to a series of novel quaternary silicone polymers. These polymers have a pendant quaternary nitrogen functional group present. The polymers by virtue of the pendent group deposit on hair, skin and fiber surfaces forming effective nonvolatile nonirritating, surface modifying finishes. The compounds of the present invention are excellent conditioners, antistats and non-yellowing, softeners. The compounds of this invention are represented by the following formula; chloride. l5 R-0-C(0)--CHI-R' Class #4. Amido amine salts derived from partially acid neutralized amines. wherein It is known that under certain catalytic conditions, R is epichlorohydrin reacts with certain alcohols to give an intermediate which can be used to react with tertiary amines to quaternary compounds. U.S. Pat. No. 30 3,445,440 to Susi (May 1969) and U.S. Pat. No. 3,517,045 to Susi (June 1970) teaches the use of chlorohydroxypropyl ether to alkylate specific tertiary amines which are the reaction product of a primary fatty amine and ethylene or propylene oxide. The com- 35 pounds are used as antistatic agents in polymeric compositions such as polyolefin. The antistatic properties of these compounds are achieved by the minimization of static charges on the polymer surface. These anti-static materials are incorporated into the polymer melt and 40 are effective by virtue of their insolubility in the molten polymer. The quaternary compounds migrate to the polymer surface and are effective antistatic agents. U.S. Pat. No. 4,144,122 to Emanuelsson issued Mar. 13, 1979 teaches that tallow alcohol and certain other 45 higher molecular weight non-guerbet alcohols and their alkoxylates can be reacted with epichlorohydrin, then subsequently with tertiary amines to give compounds suitable for paper debonding. U.S. Pat. No. 4,215,064 to Lindemann et a1 issued Jul. 50 29, 1980 teaches that phosphobetaines can be prepared by the reaction of a phosphate or phosphite salt with epichlorohydrin under aqueous conditions. U.S. Pat. No. 4,283,541 to O'Lenick, et al, issued Aug. 11, 1981 teaches the process for the preparation of the phos- 55 phobetaines described in Lindemann (U.S. Pat. No. 4,215,064). None of these patents teach the compounds of the present invention. U.S. Pat. No. 4.800.077 issued Jan. 1989 to O'Lenick , , teaches guerbet alcohol quaternary compounds can be 60 prepared by reacting epichlorohydrin with guerbet alcohols then subsequently reacting the intermediate with arnines. None of the above incorporate silicone into the quaternary compound. Consequently, the unique softening 65 and substantivity properties achieved using the compounds of the present invention are not realized with the above technologies. a is an integer from 0 to 200; b is an integer from 0 to 200; c is an integer from 1 to 200; Rl is selected from -(CH2),CH3 or phenyl; n is an integer from 0 to 10; R2 is -(CH~)~-(OCH~CH~)X-(OCH~CH(CH~- ))y-(OCH2CH2)z-OH; x, y and z are integers and are independently selected from 0 to 20; R' is selected from R3, R4, and R5 are each independently alkyl having from 1 to 20 carbon atoms; R6 is alkyl having from 6 to 20 carbon atoms; R7 and R8 are independently selected from methyl and ethyl; or wherein R9 is alkyl having from 6 to 20 carbon atoms; v is an integer from 1 to 5. The products of the present invention are prepared by reaction of a hydroxyl containing silicone polymer with a halo acid, most commonly chloracetic acid resulting in a halo ester which in a subsequent step is reacted with an amine to give the desired quaternary compounds which can be used to make the products of compounds. this invention. CH2=CH-CH2-O-(CH2-CH24)~-(CH2-~~(~~3)-0)Y-(~~2-~~2-0)z-~ Molecular Designation x Y z Weight DIMETHICONE COPOLYOL HALO-ESTER PREPARATION OF INTERMEDIATES INTERMEDIATE Silicone intermediates of the type used to make the The intermediate silicone copolyol halo-ester is an compounds of this invention are well known to those additional aspect of the present invention. It is useful as skilled in the art. International Publication (Silicone an intermediate in the preparation of the compounds of 20 Alkylene Oxide Copolymers As Foam Control Agents) the present invention. WO 86/0541 by Paul Austin Sep. 25, 1986) p. 16 (exam- R"O-(CH~CH~O)~-(CH~CH(CH~)O)~-(CH~CH~O)X-(CH~)~ CH3 H20 and C H 3C-I H~3 O - ~ O - [ ~ O ! 7 T O - ~ i - C HC3H 3 C1 H3 wherein R" is -C(O)-CH2-Cl; a is an integer from 0 to 200: ples 1 to 6) is one of many references which teaches how to make the following intermediates. b is an integer from 0 to 200'; c is an integer from 1 to 200; 40 HYDROSILATION OF INTERMEDIATES R' is selected from -(CH2),CH3 or phenyl; Silanic Hydrogen Containing Compounds n is an integer from 0 to 10; R2 is -(CH2)3-(OCH2CH2)x-(OCHzCH(CH3- ))y-(OCH2CH2)z-OH; CH3 CH3 CH3 CH3 45 I I I I x, y and z are integers and are independently selected CH~-si-0-si-0-si-0-si-CH~ from 0 to 20. CI H3 CI H3 H1 CIH 3 The compounds of the related invention of which this is a continuation in part are based upon the reaction of M I D I D * I M epichlorohydrin with a dimethicone copolyol. We have unecxpectantly found that the esterification reaction of Group Desimations the dimethicone copolyol is easier and results in im- Average Equivalent Austin Group Molecular Molecular proved purity. The ester linkage also results in some- ~~~~~l~ ~~~~~l~ ~ ~ Weiight ~Weight ~ ~ ~ what improved solubility of the quat in polar solvents. 1 1 MD20 D'3.2 M 1,850 551 DIMETHICONE COPOLYOL REACTANTS 55 : 4 MDlmD'5 M 24,158 4,831 6 MD20 D.10 M 2,258 225 One method of ~.r e.~ a r-i tnhge reactive hvdroxvl containing silicone polymer is to react silanic hydrogen containing polymer with ally1 alcohol or ally1 alcohol HYDROSILATION COMPOUNDS alkoxylate monomer. Procedures this reaction are well 60 The hydrosilation reaction used to make the known those '' the art. Pat. No. pounds of this invention are well known to those skilled 4,083,856 describe suitable processes. in the art. Reference; International Publication (Silicone EXAMPLES Vinvl Intermediate Com~ounds Alkylene Oxide CopoIymers As Foam Control- ~ ~ e n t s ) WO 86/0541 by Paul Austin (Sep. 25, 1986) p.19. LC 0 J Compounds of this class are prepared by alkoxylation EXAMPLE 4 of allyl alcohol using methods well known to those To a 22 liter three necked round bottom flask fitted skilled in the art. The following are some of the many with a mechanical agitator, thermometer with a Thermo- watch temperature regulator, nitrogen sparge tube vented reflux condenser and heating mantle is added 189.0 grams of Vinyl Intermediate Example #A. Next add 225 grams of Silanic Hydrogen Containing Compound Example #3 and 3,000 grams of toluene. Heat to 5 115 C. to remove azeotropically remove any water and 200 ml of toluene. The temperature is reduced to 85 C. and 3.5 ml of 3% H2PtC16 in ethanol is added. Light to then excluded from the flask by covering it with a black cloth. An exotherm is noted to about 95 C., while the lo contents are stirred for about 2 hours. During this time Grams of Grams of Calalyst Dimethicone Copolyol Chloroacetic Stannous Example Example # Grams Acid SnO Oxylate 1 1 4 740.0 94.0 4 0 12 5 7009.0 94.0 2 2 13 6 943.0 94.0 0 4 14 7 608.0 94.0 4 0 I5 8 7771.0 94.0 2 2 16 9 1105.0 94.0 0 4 silanic hydrogen concentration drops to nil. cool to 65 17 10 202 I .o 94.0 4 o C. and slowlv add 60 a of sodium bicarbonate. allow to mix overnight and filter through a 4 micron pad. Distill off any toluene at 100 C. and 1 torr. l5 QUATERNARY REACTION SEQUENCE EXAMPLE 5-10 All amine reactants are commercially available from Tomah Products Division of Exxon Chemicals Milton The above procedure is repeated, only this time replacing both the silanic hydrogen compound #3 with 20 Wi. the specified number of grams of the specified silanic hydrogen compound and the vinyl intermediate exam- ple A with the specified number of grams of the speci- /R3 R ~ O C ( 0 ) C H 2 ~ C I + N-R4 + tied vinyl intermediate. 25 'R5 Silanic CRR~ Vinyl Intermediate Hydrogen Compound Examole Examole Grams Examole Grams PREPARATION OF THE SILICONE HYDROXYPROPYLETHER HALIDE Reaction Sequence R-OH + HO-C(0)-CH2CI R contains the silicone portion of the molecule The following examples further illustrate the objects and advantages of this invention, though it should be understood that the various reactants and amounts thereof, reaction conditions, and other details are merely illustrative and should not be construed to unduly limit this invention. AMINE REACTANT GROUP 1 The reactants are tertiary amines conforming to the following structure; R contains the silicone portion of the molecule. Example Number R3 R4 R S 50 The following examples further illustrate the objects 18 C10H21 CH3 CH3 19 and advantages of this invention, though it should be C1zH2s CH3 CH3 20 Ci4Hz9 CH3 CH3 understood that the various reactants and amounts 2 I c1c.H~ CH3 CH3 thereof. reaction conditions. and other details are 22 CIRHJ~ CH3 CH1 merely illustrative and should not be construed to un- 55 duly limit this invention. General Procedure 26 C14H29 CZOQI CH3 27 C16H33 c10Hz1 CH3 Place the indicated amount of the dimethicone copo- 28 C18H37 CIZH~S CH3 lyol produced by the example shown in a suitable ves- 60 29 C2&1 Ci4Hz9 CH3 sel. Add the desired amount of catalyst as shown under 30 W I ~ W I ~ -13 good agitation and a nitrogen sparge. The specified 3 I C2H5 CH3 C2Hs amount of monochloracetic acid is added. A molar 32 c1oH21 c10H21 c10Hz1 excess of 0.1 to 0.5 of chloracetic acid is added. The temperature is held between 160-200 degrees C. for two 65 to six hours. Reaction progress is monitored by acid AMINE REACTANT GROUP 2 value analysis and at the end of the reaction reaches The reactants are amido tertiary amines conforming theoretical for the mole ratio used. to the following structure; R7 Amine Reactants Silicone Reactants Water 6 I Example Example Grams Example Grams Grams R-c(o)N(H)-(CH~)~-N-R~ 5 63 21 253.0 14 702.0 955.0 Example Number R6 R7 R8 64 22 279.0 15 7,865.0 8,144.0 65 23 305.0 16 1,119.0 1,424.0 AMINE REACTANT GROUP 3 87 45 4,928.0 17 3,155.0 8,083.0 25 88 46 300.0 11 834.0 1,134.0 The reactants are imidazoline compounds conform- 89 47 328.0 12 7,103.0 7,431.0 90 48 1,782.0 13 ing to the following structure; 9 I 49 1,370.0 1143 1,700327..00 22,,801792..00 92 50 1,103.0 15 7,865.0 8,968.0 93 51 1,131.0 16 1,119.0 2,250.0 (CH212 - N 30 94 52 184.0 17 3,155.0 3,339.0 I 11 95 53 212.0 11 834.0 1,046.0 N--c-R9 96 54 240.0 12 7,103.0 7,343.0 I 97 55 268.0 13 1,037.0 1,305.0 CHzCHzOH 98 56 296.0 14 702.0 998.0 99 57 324.0 15 7,865.0 8,189.0 Example Number R9 58 352.0 16 1,119.0 1,471.0 35 :: 52 CsHl I 59 380.0 17 3,155.0 3,535.0 53 C7His 54 C9H19 55 CllH23 56 C13H27 APPLICATIONS EVALUATION 57 CISH~I 40 Applications of the Compounds of The Invention 58 C17H35 59 C19H39 Compounds of this invention were compared to standard compounds commercially available using AATCC Test Method 117-1979. The color fastness heat test uses GENERAL REACTION PROCEDURE a 400 F. (205 F.) hot iron which is applied for 60 and 180 The products of the present invention are generally 45 seconds.~hec olor is rated on a 1 5b asis for yellow- ~. r e. ~ a r eind aaueous solution or dis~ersion.T he Dre- ness, (5 being the most yellow). ferred concentration is about 50% solids. Additionally, alcohols such as methanol, ethanol, isopropanol, glycols such as ethylene glycol, propylene glycol, polypropyl- 50 ene glycol, polyethylenegylcol, hexylene glycol, and cyclomethicone can be added to improve clarity if desired. To a suitable flask, equipped with a thermometer and agitator is added the specified amount of water. Next 55 add the specified amount of the type of silicone reactant. Heat to 50 C. Next add the specified amount of the specified amine under good agitation. THe reaction mass is heated to 85-95 C. and held from between 5 and Compound CAS Number

    Yellowness Stearyl Imidazoline Quat 68122-86-1 4 (Alkaquat ST) Distearyl Quat 61789-81-9 4 Tallow Amido Quat 65098-88-6 5 (Alkaquat DAET-90) Stearyl Amido Propyl Salt 68308-45-2 4 Example 63 1 Examole 92 2 WET COMB OUT TEST l5 hours. The progress is monitored % 60 A laboratory test is conducted to screen the wet inorganic chloride, which approaches 98% of theoreti- comb Droverties of a member of the famcal. ily of novel compounds. Hair swatches are purchased from a supply of human hair from the same head. Each Reactants silicone R~~~~~~~ water test swatch contains 7 grams of hair and is 11 inches in ~~~~~l~ ~~~~~l~ G~~~~ ~~~~~l~ G~~~~ G~~~~ 65 length. The hair is tied tightly 1 inch from one end with 60 18 185.0 11 834.0 1,019,0 string. THe swatch is pre-cleaned with a 3% solution of 61 19 201.0 12 7,103.0 ammonium lauryl sulfate. Subsequently, the swatch is 62 20 227.0 13 1,037.0 1,264.0 washed under running tap water. The hair is then squeezed out and while still damp dipped into a 200 ml R"O-(CHzCH20);-(CH2CH(CH3)O),--(CH2CH2O),--(CH2)3 solution of 0.29% active auaternarv. Another rinse is - -. ,- ,- 1 - made, then the swatch is blotted dry. The swatch is then treated by holdiqg the hair swatch, combing the hair as rapidly as possible while alternating the side of the - L J o L J b L CH3 swatch combed. The time needed to get one smooth 10 free stroke without tangling is recorded. Typical results for the standard quaternary compounds used in hair conditioning (stearyldimethylbenzyl ammonium chlo- wherein; 15 R" is -C(O)-CH2-CI; ride) range frop 12-14 seconds. a is an integer from 0 to 200; b is an integer from 0 to 200, c is an integer from 1 to 200, Xinse Conditioner (Wet Comb Out Test) R1 is -(cH~),cH~ or phenyl; 20 n is an integer from 0 to 10; PrMuct Time in Seconds R2 is -(CH2)3-(OCH2CH2)x-(OCH2CH(CH3- ))y-(OCH2CH2)z-OH; Product Example 60 11 x, y and z are integers which independently range Product Example 92 13 from 0 to 20. Stearyldimethylbenryl 12 25 2. A compound of claim 1 wherein x is 3, y is 0, and z is 0. ammonium chloride 3. A compound of claim 1 wherein x is 9, y is 27, and z is 3. 4. A compound of claim 1 wherein x is 11, y is 3, and As can be seen, the compounds of the invention give 30 is 0. significant conditioning properties to hair, and coupled 5. A wherein is O, y is 0* and z is 0. with their mild nature with regard to skin and eyes, 6. A compound of claim 1 wherein x is 20, y is 20, and makes it a prime candidate for cosmetic applications. is 20. 35 7. A compound of claim 1 wherein x is 20, y is 0, and I claim: z is 0. 1. A dimethicone copolyol halo ester intermediate 8. A compound of claim 1 wherein x is 10, y is 10, and z is 10. which conforms to the following strupure; 40
×
×
  • 创建新的...