丙烯酸

常用名 丙烯酸 英文名 Glacial Acrylic Acid
CAS号 79-10-7 分子量 72.063
密度 1.1±0.1 g/cm3 沸点 141.0±0.0 °C at 760 mmHg
分子式 C3H4O2 熔点 13 °C(lit.)
MSDS丙烯酸的MSDS|SDS|pdf下载 中文版 美版 闪点 54.4±0.0 °C
符号 GHS02 GHS05 GHS07 GHS09
GHS02, GHS05, GHS07, GHS09
信号词 Danger

 丙烯酸用途


1.丙烯酸及其系列产品,主要是其酯类,近年得到迅速发展。如象乙烯、丙烯、氯乙烯、丙烯腈等那样,发展成为重要的高分子化学工业的原料。丙烯酸及其酯类作为高分子化合物的单体,世界总产量已超过百万t,而由其制成的聚合物和共聚物(主要是乳液型树脂)的产量将近500万t。这些树脂的应用遍及涂料,塑料、纺织、皮革、造纸、建材,以及包装材料等众多部门。丙烯酸及其酯类可供有机合成和高分子合成,而绝大多数是用于后者,并且更多地是与其他单体,如乙酸乙烯、苯乙烯、甲基丙烯酸甲酯等进行共聚,制得各种性能的合成树酯、功能高分子材料和各种助剂等。

2.主要应用领域:(1)经纱上浆料 由丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯腈、聚丙烯酸铵等原料配制的经纱上浆料,比聚乙烯醇上浆料容量退浆,节省淀粉。

(2)胶粘剂 用丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸-2-乙基己酯等共聚乳胶,可作静电植绒、植毛的胶粘剂,其坚牢性和手感好。

(3)水稠化剂 用丙稀酸和丙烯酸乙酯共聚物制成高分子量的粉末。可作稠化剂,用于油田,每吨产品可增产500t原油,对老井采油效果较好。

(4)铜版纸涂饰剂 用丙烯酸、丙烯酸丁酯、丙烯酸-2-乙基己酯、苯乙烯等四元共聚乳胶作铜版纸涂料,保色不泛黄,印刷性能好,不粘辊,比丁苯胶乳好可节省干酷素。

(5)聚丙烯酸盐类 利用丙烯酸可生产各种聚丙烯酸盐类产品(如铵盐、钠盐、钾盐、铝盐、镍盐等)。用作凝集剂、水质处理剂、分散剂、增稠剂、食品保鲜剂耐酸碱干燥剂,软化剂等各种高分子助剂。

3.重要的有机合成原料及合成树脂单体,是聚合速度非常快的乙烯类单体。大多数用以制造丙烯酸甲酯、乙酯、丁酯、羟乙酯等丙烯酸酯类。丙烯酸及丙烯酸酯可以均聚及共聚,也可以与丙烯腈、苯乙烯、丁二烯、氯乙烯及顺酐等单体共聚。其聚合物用于合成树脂、胶黏剂、合成橡胶、合成纤维、高吸水性树脂、制药、皮革、纺织、化纤、建材、水处理、石油开采、涂料等工业部门。丙烯酸是水溶性聚合物的重要原料之一,与淀粉接枝共聚可制得超强性吸水剂。

4.丙烯酸树脂的制备,橡胶合成,涂料制备,制药工业。

5.用于树脂制造。

更多

 丙烯酸物理化学性质

[ 密度 ]: 1.1±0.1 g/cm3
[ 沸点 ]: 141.0±0.0 °C at 760 mmHg
[ 熔点 ]: 13 °C(lit.)
[ 分子式 ]: C3H4O2
[ 分子量 ]: 72.063
[ 闪点 ]: 54.4±0.0 °C
[ 精确质量 ]: 72.021126
[ PSA ]: 37.30000
[ LogP ]: 0.28
[ 外观性状 ]: 无色液体
[ 蒸汽密度 ]: 2.5 (vs air)
[ 蒸汽压 ]: 3.4±0.5 mmHg at 25°C
[ 折射率 ]: 1.422
[ 储存条件 ]:

1.密封阴凉避光保存。远离火种、热源,防水、防潮、防冻。贮存温度最好在15-20℃之间。为防止贮存时冻结,一般使其水溶液含量保持在80%(凝固点-5.5℃)或用溶剂稀释。

2.采用聚乙烯衬里的铁桶包装,每桶重200kg,也可用不锈钢或碳钢贮槽,但必须防止水分和湿气,以防生锈造成丙烯酸聚合。在贮存和运输时都要添加200*10-6的阻聚剂。按“腐蚀性化学品规定”贮运。

3.储存注意事项通常商品加有阻聚剂。储存于阴凉、通风的库房。远离火种、热源。库温不宜超过5℃(装于受压容器中例外)。包装要求密封,不可与空气接触。应与氧化剂、碱类分开存放,切忌混储。不宜大量储存或久存。采用防爆型照明、通风设施。禁止使用易产生火花的机械设备和工具。储区应备有泄漏应急处理设备和合适的收容材料。

[ 稳定性 ]:

1.化学性质活泼,遇光、热、过氧化物等容易发生聚合。有较强的腐蚀性,易燃。受热易分解产生有毒气体。具有双键及羧基官能团的联合反应,可发生加成反应、官能团反应以及酯交换反应。常用以制备多环和杂环化合物。易被氢还原成丙酸,遇碱能分解成甲酸和乙酸。

2.本品有较强的腐蚀性,中等毒性。其水溶液或高浓度蒸气会刺激皮肤和黏膜。大鼠口服LD50为590mg/kg。注意不得与丙烯酸溶液或蒸汽接触,操作时要佩戴好工作服和工作帽、防护眼镜和胶皮手套。生产设备应密闭。工作和贮存场所要具有良好的通风条件。

3.稳定性 稳定

4.禁配物 强氧化剂、强碱

5.避免接触的条件 受热、光照、接触空气

6.聚合危害 聚合

[ 水溶解性 ]: MISCIBLE
[ 分子结构 ]:

1、摩尔折射率:17.23

2、摩尔体积(cm3/mol):67.7

3、等张比容(90.2K):162.3

4、表面张力(dyne/cm):32.8

5、极化率(10-24cm3):6.83

[ 计算化学 ]:

1、疏水参数计算参考值(XlogP):0.3

2、氢键供体数量:1

3、氢键受体数量:2

4、可旋转化学键数量:1

5、拓扑分子极性表面积(TPSA):37.3

6、重原子数量:5

7、表面电荷:0

8、复杂度:55.9

9、同位素原子数量:0

10、确定原子立构中心数量:0

11、不确定原子立构中心数量:0

12、确定化学键立构中心数量:0

13、不确定化学键立构中心数量:0

14、共价键单元数量:1

[ 更多 ]:

1.性状:无色液体,有刺激性气味。

2.熔点(℃):13

3.沸点(℃):141

4.相对密度(水=1):1.05

5.相对蒸气密度(空气=1):2.45

6.饱和蒸气压(kPa):1.33(39.9℃)

7.燃烧热(kJ/mol):-1366.9

8.临界压力(MPa):5.66

9.辛醇/水分配系数:0.36

10.闪点(℃):54(CC);54.5(OC)

11.引燃温度(℃):360

12.爆炸上限(%):8.0

13.爆炸下限(%):2.4

14.溶解性:与水混溶,可混溶于乙醇、乙醚。

15.黏度(mPa·s,25ºC):1.149

16.汽化热(KJ/mol):45.6

17.熔化热(KJ/mol,13ºC):11.1

18.相对密度(20℃,4℃):1.050

19.相对密度(25℃,4℃):1.044

20.常温折射率(n20):1.422

21.溶度参数(J·cm-3)0.5:26.229

22.van der Waals面积(cm2·mol-1):6.000×109

23.van der Waals体积(cm3·mol-1):39.930

24.液相标准燃烧热(焓)(kJ·mol-1):-1368.43

25.液相标准声称热(焓)( kJ·mol-1):-383.76

26.液相标准熵(J·mol-1·K-1) :226.4

27.液相标准热熔(J·mol-1·K-1):144.2

28.气相标准燃烧热(焓)(kJ·mol-1):-1428.7

29.气相标准声称热(焓)( kJ·mol-1) :-323.5

30.气相标准熵(J·mol-1·K-1) :307.73

31.气相标准生成自由能( kJ·mol-1):-271.0

32.气相标准热熔(J·mol-1·K-1):81.80

 丙烯酸MSDS

国标编号: 81617
CAS: 79-10-7
中文名称: 丙烯酸
英文名称: Acrylic acid;Propenoic acid
别 名:
分子式: C3H4O2;CH2CHCOOH
分子量: 72.06
熔 点: 14℃ 沸点:141℃
密 度: 相对密度(水=1)1.05;
蒸汽压: 50℃
溶解性: 与水混溶,可混溶于乙醇、乙醚
稳定性: 稳定
外观与性状: 无色液体,有刺激性气味
危险标记: 20(酸性腐蚀品)
用 途: 用于树脂制造

2.对环境的影响:
一、健康危害
侵入途径:吸入、食入、经皮吸收。
健康危害:本品对皮肤、眼睛和呼吸道有强烈刺激作用。
二、毒理学资料及环境行为
毒性:属低毒类。
急性毒性:LD 502520mg/kg(大鼠经口);950mg/kg(兔经皮);LC 505300mg/m 3,2小时(小鼠吸入)
致突变性:细胞遗传学分析:小鼠淋巴细胞450mg/L。
生殖毒性:大鼠腹腔最低中毒剂量(TDL 0):73216ug/kg(孕5~15天),致胚胎毒性,肌肉骨骼发育异常。
致癌性:IARC致癌性评论:动物、人类皆无可靠数据。
危险特性:其蒸气与空气形成爆炸性混合物,遇明火、高热能引起燃烧爆炸。与氧化剂能发生强烈反应。若遇高热,可能发生聚合反应,出现大量放热现象,引起容器破裂和爆炸事故。
燃烧(分解)产物:一氧化碳、二氧化碳。

3.现场应急监测方法:


 

4.实验室监测方法:


气相色谱法《气相色谱法测定环境大气中丙烯酸酯类化合物》顾海东等,上海环境监测,1998(1)P115~16

5.环境标准:

前苏联 车间空气中有害物质的最高容许浓度 5mg/m3
前苏联(1975) 水体中有害物质最高允许浓度 0.5mg/L
  嗅觉阈浓度 0.094ppm

6.应急处理处置方法:


一、泄漏应急处理
疏散泄漏污染区人员至安全区,禁止无关人员进入污染区,切断火源。建议应急处理人员戴自给式呼吸器,穿化学防护服。不要直接接触泄漏物,在确保安全情况下堵漏。喷水雾能减少蒸发但不要使水进入储存容器内。用沙土或其它不燃性吸附剂混合吸收,然后收集运至废物处理场所处置。如大量泄漏,利用围堤收容,然后收集、转移、回收或无害处理后废弃。
二、防护措施
呼吸系统防护:空气中浓度超标时,应该佩带防毒面具。紧急事态抢救或逃生时,佩带自给式呼吸器。
眼睛防护:戴化学安全防护眼镜。
防护服:穿工作服(防腐材料制作)。
手防护:戴橡皮手套。
其它:工作后,淋浴更衣。注意个人清洁卫生。
三、急救措施
皮肤接触:脱去污染的衣着,立即用水冲洗至少15分钟。
眼睛接触:立即提起眼睑,用流动清水或生理盐水冲洗至少15分钟。
吸入:迅速脱离现场至空气新鲜处。保持呼吸道通畅。必要时进行人工呼吸。就医。
食入:误服者给饮大量温水,催吐,就医。
灭火方法:雾状水、二氧化碳、砂土、抗溶性泡沫。

 丙烯酸毒性和生态

丙烯酸毒理学数据:

1.急性毒性

LD50:2520mg/kg(大鼠经口);2400mg/kg(小鼠经口);950mg/kg(兔经皮)

LC50:1200ppm(大鼠吸入,4h);5300mg/m3(小鼠吸入,2h)

2.刺激性

家兔经皮:500mg,重度刺激(开放性刺激试验)。

家兔经眼:250μg(24h),重度刺激。

3.致突变性 细胞遗传学分析:小鼠淋巴细胞450mg/L。哺乳动物体细胞突变:小鼠淋巴细胞500mg/L。细胞遗传学分析:仓鼠卵巢116mg/L。

4.致癌性 IARC致癌性评论:G3,对人及动物致癌性证据不足。

5.其他 大鼠腹腔最低中毒剂量(TDLo):73216μg/kg(孕5~15d),致胚胎毒性,肌肉骨骼发育异常。

丙烯酸生态学数据:

1.生态毒性

IC50:41mg/L(72h)(藻类)

2.生物降解性

好氧生物降解(h):24~168

厌氧生物降解(h):672~4320

3.非生物降解性

光解最大光吸收(nm):250

空气中光氧化半衰期(h):2.5~23.8

CHEMICAL IDENTIFICATION

RTECS NUMBER :
AS4375000
CHEMICAL NAME :
Acrylic acid
CAS REGISTRY NUMBER :
79-10-7
BEILSTEIN REFERENCE NO. :
0635743
LAST UPDATED :
199806
DATA ITEMS CITED :
55
MOLECULAR FORMULA :
C3-H4-O2
MOLECULAR WEIGHT :
72.07
WISWESSER LINE NOTATION :
QV1U1

HEALTH HAZARD DATA

ACUTE TOXICITY DATA

TYPE OF TEST :
Open irritation test
ROUTE OF EXPOSURE :
Administration onto the skin
SPECIES OBSERVED :
Rodent - rabbit
TYPE OF TEST :
Standard Draize test
ROUTE OF EXPOSURE :
Administration onto the skin
SPECIES OBSERVED :
Rodent - rabbit
TYPE OF TEST :
Standard Draize test
ROUTE OF EXPOSURE :
Administration into the eye
SPECIES OBSERVED :
Rodent - rabbit
TYPE OF TEST :
Standard Draize test
ROUTE OF EXPOSURE :
Administration into the eye
SPECIES OBSERVED :
Rodent - rabbit
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
33500 ug/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LCLo - Lowest published lethal concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
4000 ppm/4H
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Intraperitoneal
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
22 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Unreported
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
1250 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Rodent - mouse
DOSE/DURATION :
2400 mg/kg
TOXIC EFFECTS :
Tumorigenic - active as anti-cancer agent
TYPE OF TEST :
LC50 - Lethal concentration, 50 percent kill
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Rodent - mouse
DOSE/DURATION :
5300 mg/m3/2H
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Intraperitoneal
SPECIES OBSERVED :
Rodent - mouse
DOSE/DURATION :
144 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Subcutaneous
SPECIES OBSERVED :
Rodent - mouse
DOSE/DURATION :
1590 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Unreported
SPECIES OBSERVED :
Rodent - mouse
DOSE/DURATION :
830 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LC - Lethal concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Primate - monkey
DOSE/DURATION :
>75 ppm/6H
TOXIC EFFECTS :
Sense Organs and Special Senses (Olfaction) - deviated nasal septum Sense Organs and Special Senses (Olfaction) - ulcerated nasal septum
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Administration onto the skin
SPECIES OBSERVED :
Rodent - rabbit
DOSE/DURATION :
280 uL/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
LD50 - Lethal dose, 50 percent kill
ROUTE OF EXPOSURE :
Unreported
SPECIES OBSERVED :
Rodent - rabbit
DOSE/DURATION :
250 mg/kg
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
TYPE OF TEST :
TDLo - Lowest published toxic dose
ROUTE OF EXPOSURE :
Oral
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
22500 mg/kg/90D-C
TOXIC EFFECTS :
Behavioral - fluid intake Kidney, Ureter, Bladder - changes in bladder weight Related to Chronic Data - changes in testicular weight
TYPE OF TEST :
TCLo - Lowest published toxic concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
223 ppm/6H/2W-I
TOXIC EFFECTS :
Sense Organs and Special Senses (Olfaction) - effect, not otherwise specified Nutritional and Gross Metabolic - weight loss or decreased weight gain
TYPE OF TEST :
TCLo - Lowest published toxic concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
75 ppm/6H/13W-I
TOXIC EFFECTS :
Sense Organs and Special Senses (Olfaction) - effect, not otherwise specified
TYPE OF TEST :
TCLo - Lowest published toxic concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Rodent - mouse
DOSE/DURATION :
223 ppm/6H/2W-I
TOXIC EFFECTS :
Sense Organs and Special Senses (Olfaction) - effect, not otherwise specified Nutritional and Gross Metabolic - weight loss or decreased weight gain
TYPE OF TEST :
TCLo - Lowest published toxic concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Rodent - mouse
DOSE/DURATION :
25 ppm/6H/13W-I
TOXIC EFFECTS :
Sense Organs and Special Senses (Olfaction) - effect, not otherwise specified Nutritional and Gross Metabolic - weight loss or decreased weight gain
TYPE OF TEST :
TDLo - Lowest published toxic dose
ROUTE OF EXPOSURE :
Administration onto the skin
SPECIES OBSERVED :
Rodent - mouse
DOSE/DURATION :
37440 mg/kg/78W-I
TOXIC EFFECTS :
Tumorigenic - Carcinogenic by RTECS criteria Blood - leukemia
TYPE OF TEST :
TDLo - Lowest published toxic dose
ROUTE OF EXPOSURE :
Subcutaneous
SPECIES OBSERVED :
Rodent - mouse
DOSE/DURATION :
2912 mg/kg/52W-I
TOXIC EFFECTS :
Tumorigenic - equivocal tumorigenic agent by RTECS criteria Tumorigenic - tumors at site of application
TYPE OF TEST :
TD - Toxic dose (other than lowest)
ROUTE OF EXPOSURE :
Administration onto the skin
SPECIES OBSERVED :
Rodent - mouse
DOSE/DURATION :
37440 mg/kg/78W-I
TOXIC EFFECTS :
Tumorigenic - equivocal tumorigenic agent by RTECS criteria Skin and Appendages - tumors
TYPE OF TEST :
TDLo - Lowest published toxic dose
ROUTE OF EXPOSURE :
Oral
DOSE :
169 gm/kg
SEX/DURATION :
male 13 week(s) pre-mating female 13 week(s) pre-mating - 3 week(s) post-birth
TOXIC EFFECTS :
Reproductive - Paternal Effects - testes, epididymis, sperm duct Reproductive - Effects on Newborn - growth statistics (e.g.%, reduced weight gain) Reproductive - Effects on Newborn - physical
TYPE OF TEST :
TDLo - Lowest published toxic dose
ROUTE OF EXPOSURE :
Intraperitoneal
DOSE :
14340 ug/kg
SEX/DURATION :
female 5-15 day(s) after conception
TOXIC EFFECTS :
Reproductive - Specific Developmental Abnormalities - other developmental abnormalities
TYPE OF TEST :
TDLo - Lowest published toxic dose
ROUTE OF EXPOSURE :
Intraperitoneal
DOSE :
7329 ug/kg
SEX/DURATION :
female 5-15 day(s) after conception
TOXIC EFFECTS :
Reproductive - Effects on Embryo or Fetus - fetotoxicity (except death, e.g., stunted fetus) Reproductive - Specific Developmental Abnormalities - musculoskeletal system

MUTATION DATA

TYPE OF TEST :
Cytogenetic analysis
TEST SYSTEM :
Rodent - hamster Ovary
REFERENCE :
FCTOD7 Food and Chemical Toxicology. (Pergamon Press Inc., Maxwell House, Fairview Park, Elmsford, NY 10523) V.20- 1982- Volume(issue)/page/year: 30,505,1992 *** REVIEWS *** ACGIH TLV-Not classifiable as a human carcinogen DTLVS* The Threshold Limit Values (TLVs) and Biological Exposure Indices (BEIs) booklet issues by American Conference of Governmental Industrial Hygienists (ACGIH), Cincinnati, OH, 1996 Volume(issue)/page/year: TLV/BEI,1997 ACGIH TLV-TWA 5.9 mg/m3 (2 ppm) (skin) DTLVS* The Threshold Limit Values (TLVs) and Biological Exposure Indices (BEIs) booklet issues by American Conference of Governmental Industrial Hygienists (ACGIH), Cincinnati, OH, 1996 Volume(issue)/page/year: TLV/BEI,1997 IARC Cancer Review:Animal No Adequate Data IMEMDT IARC Monographs on the Evaluation of Carcinogenic Risk of Chemicals to Man. (WHO Publications Centre USA, 49 Sheridan Ave., Albany, NY 12210) V.1- 1972- Volume(issue)/page/year: 19,47,1979 IARC Cancer Review:Human No Adequate Data IMEMDT IARC Monographs on the Evaluation of Carcinogenic Risk of Chemicals to Man. (WHO Publications Centre USA, 49 Sheridan Ave., Albany, NY 12210) V.1- 1972- Volume(issue)/page/year: 19,47,1979 IARC Cancer Review:Group 3 IMSUDL IARC Monographs, Supplement. (WHO Publications Centre USA, 49 Sheridan Ave., Albany, NY 12210) No.1- 1979- Volume(issue)/page/year: 7,56,1987 *** OCCUPATIONAL EXPOSURE LIMITS *** OEL-AUSTRALIA:TWA 10 ppm (30 mg/m3) JAN 1993 OEL-BELGIUM:TWA 10 ppm (29 mg/m3) JAN 1993 OEL-DENMARK:TWA 10 ppm (30 mg/m3) JAN 1993 OEL-FRANCE:TWA 10 ppm (30 mg/m3) JAN 1993 OEL-THE NETHERLANDS:TWA 10 ppm (30 mg/m3) JAN 1993 OEL-RUSSIA:STEL 5 mg/m3 JAN 1993 OEL-SWEDEN:TWA 10 ppm (30 mg/m3);STEL 15 ppm (45 mg/m3) JAN 1993 OEL-SWITZERLAND:TWA 10 ppm (30 mg/m3) JAN 1993 OEL-UNITED KINGDOM:TWA 10 ppm (30 mg/m3);STEL 20 ppm (60 mg/m3) JAN 1993 OEL IN BULGARIA, COLOMBIA, JORDAN, KOREA check ACGIH TLV OEL IN NEW ZEALAND, SINGAPORE, VIETNAM check ACGIH TLV *** NIOSH STANDARDS DEVELOPMENT AND SURVEILLANCE DATA *** NIOSH RECOMMENDED EXPOSURE LEVEL (REL) : NIOSH REL TO ACRYLIC ACID-air:10H TWA 2 ppm (Sk) REFERENCE : NIOSH* National Institute for Occupational Safety and Health, U.S. Dept. of Health, Education, and Welfare, Reports and Memoranda. Volume(issue)/page/year: DHHS #92-100,1992 NIOSH OCCUPATIONAL EXPOSURE SURVEY DATA : NOHS - National Occupational Hazard Survey (1974) NOHS Hazard Code - 03570 No. of Facilities: 1679 (estimated) No. of Industries: 44 No. of Occupations: 41 No. of Employees: 28576 (estimated) NOES - National Occupational Exposure Survey (1983) NOES Hazard Code - 03570 No. of Facilities: 4826 (estimated) No. of Industries: 74 No. of Occupations: 67 No. of Employees: 96535 (estimated) No. of Female Employees: 28146 (estimated)

 丙烯酸安全信息

[ 符号 ]: GHS02 GHS05 GHS07 GHS09
GHS02, GHS05, GHS07, GHS09
[ 信号词 ]: Danger
[ 危害声明 ]: H226-H302 + H312 + H332-H314-H335-H400
[ 警示性声明 ]: P210-P261-P273-P303 + P361 + P353-P304 + P340 + P310-P305 + P351 + P338
[ 个人防护装备 ]: Faceshields;full-face respirator (US);Gloves;Goggles;multi-purpose combination respirator cartridge (US);type ABEK (EN14387) respirator filter
[ 危害码 (欧洲) ]: C:Corrosive
[ 风险声明 (欧洲) ]: R10;R20/21/22;R35;R50
[ 安全声明 (欧洲) ]: S26-S36/37/39-S45-S61
[ 危险品运输编码 ]: UN 2218 8/PG 2
[ WGK德国 ]: 1
[ RTECS号 ]: AS4375000
[ 包装等级 ]: II
[ 危险类别 ]: 8
[ 海关编码 ]: 2916110000

 丙烯酸合成线路

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 丙烯酸制备

1.氰乙醇法 该法以氯乙醇和氰化钠为原料,反应生成氰乙醇,氰乙醇在硫酸存在下于175℃水解生成丙烯酸:若水解反应在甲醇中进行,则生成丙烯酸甲酯。

79-10-7 preparation

2.丙烯腈水解法 丙烯腈先以硫酸水解生成丙烯酰胺的硫酸盐,再水解生成丙烯酸,副产硫酸氢铵。此法在美国罗姆-哈斯公司得到了很大发展。

79-10-7 preparation

第一步水解温度为90~100℃。向丙烯腈中加入稍稍过量的55%~85%的硫酸,1h后丙烯腈即完全转化;然后加水进行第二次水解,并将反应温度提高到125~135℃;水解产物经减压蒸馏而得丙烯酸。此法实际上是早期氰乙醇法的发展。由于水解后生成的副产品酸性硫酸铵处理困难,原料丙烯腈的价格较贵,因而影响生产成本。

3.高压雷佩法将溶于四氢呋喃中乙炔,在溴化镍和溴化铜组成的催化剂存在下,与一氧化碳和水反应,制得丙烯酸。此法的特点是:用四氢呋喃为溶剂,可以减少高压处理乙炔的危险;同时催化剂不用原雷佩法所用的羰基镍,只需用镍盐。将丙烯与空气及水蒸气按一定摩尔比混合,在钼-铋等复合催化剂存在下,反应温度310-470℃,常压氧化制得丙烯醛,收率达90%。再将丙烯醛与空气及水蒸气按一定摩尔比混合,在钼-钒等复合催化剂存在下,反应温度300-470℃,常压氧化制得丙烯酸,收率可达98%。此法分一步和两步法。一步法是丙烯在一个反应器内氧化生成丙烯酸;两步法是丙烯先在第一反应器内氧化生成丙烯醛,丙烯醛再进入第二反应器氧化生成丙烯酸。两步法根据反应器结构,又分固定床和流化床法两种。丙烯酸的工业生产方法中,氰乙醇法,高压雷佩法已经基本淘汰,以前采用的以乙酸为原料裂解为乙烯酮,然后与无水甲醛反应生成丙内酯,再与热磷酸接触异构为丙烯酸。称烯酮法或β-丙内酯法也基本淘汰,丙烯腈法只有少数老装置采用。目前工业上采用的主要是改良雷佩法和丙烯氧化法,而后者更为普通且最有发展前途。专利报道中,还有丙酸为原料的生产方法。

4.β -丙内酯法 此法原料为乙烯酮,故又称乙烯酮法,其反应式如下:

79-10-7 preparation

先将乙酸裂解为乙烯酮,然后与无水甲醛反应生成β  丙内酯;用作催化剂在140~180℃、2.5~25MPa下,丙内酯再与热的100%磷酸接触,异构为丙烯酸。用β -丙内酯法生产丙烯酸,产品纯度高,收率亦较高,副产物和未反应物料能循环使用,并适于连续生产,但它需用乙酸为原料,特别是由于丙内酯被认为是一种致癌物质,故此法已不在工业上采用。

5.丙烯氧化法 其反应式如下:

79-10-7 preparation

将丙烯与空气及水蒸气按一定摩尔比混合,在钼铋系复合催化剂存在下,氧化制得丙烯醛,再将丙烯醛与空气及水蒸气按一定摩尔比混合,在钼-钒-钨系复合催化剂存在下,氧化制得丙烯酸。此法根据反应器结构,又分固定床法和流化床法两种。除美国索亥俄法采用流化床外,其他都采用列管式固定床。
① 固定床法。制法是:第一反应器进料丙烯含量为4%~7%,水蒸气20%~50%,其余为空气,空速1300~2600h-1,反应温度320~340℃,压力0.1~0.3MPa;第二反应器空速为1800~3600h-1,反应温度280~300℃,压力0.1~0.2MPa,丙烯和丙烯醛的转化率都在95%以上,丙烯酸的选择性以丙烯计为85%~90%。工艺过程为:使丙烯、水蒸气与经过预热的空气混合后进入第一反应器。丙烯被氧化成丙烯醛。再进入第二反应器反应,得到丙烯酸。第一、第二反应器均为列管式反应器,用熔盐作热载体,从第二反应器出来的反应气与原料空气换热后进入急冷塔,与塔顶加入的水逆向接触,获得含量为20%~30%的丙烯酸水溶液。该水溶液进入萃取塔,以乙酸丁酯或二甲苯为萃取剂,使水与丙烯酸分离。富含水的萃取液从萃取塔塔顶出来,进入溶剂回收塔,将萃取剂从塔顶蒸出,送回萃取塔循环使用。塔底排出废水。萃取塔中的萃余液进入溶剂蒸馏塔。从塔顶蒸出溶剂 (萃取剂) ,送回萃取塔循环使用;塔底得到粗丙烯酸,再经脱去轻组分和重组分后得到丙烯酸产品。丙烯经气相接触氧化反应制造丙烯酸过程中,除产物丙烯酸外,还存有微量丙烯醛、乙酸、戊酮酸、蚁酸以及其他醛类杂质。醛类是丙烯氧化副产物或由于丙烯原料中含有的杂质氧化而生成的,如乙醛、甲醛、苯甲醛、糠醛、丙烯醛等,含有这些副产物的反应气体,经冷却、抽提蒸馏后,残留于丙烯酸产品中。采用常规方法精制的丙烯酸产品中,仍含有约 (50~500) ×10-6的醛物质。为了适应高纯丙烯酸需要,北京东方化工厂以该厂聚合级丙烯酸为原料,开发出一种制备高纯丙烯酸的方法,使其总醛含量小于5×10-6,达到或超过国外有关文献报道的数据要求 ( 国外小于10×10-6) 。其实验方法是:向烧瓶中加入一定量的聚合级丙烯酸,添加试剂DL,在常压下经10~80℃范围处理后,再进入填料塔中处理蒸馏,塔釜中温度为60~80℃,塔顶温度为50~70℃,真空93.33~99.99KPa,采用补加阻聚剂及气相阻聚剂方法,可防止丙烯酸在精馏过程中聚合。用此法收集的蒸馏品即为高纯丙烯酸。
② 流化床法。制法是丙烯、空气、水经过第一沸腾床反应器生成丙烯醛,再进入第二沸腾床反应器生成丙烯酸,然后经喷淋、冷却、萃取蒸馏,再在减压塔中脱除乙酸而得丙烯酸。氧化混合物配比为丙烯∶空气∶水=1∶12∶8( 摩尔比) 。第一沸腾床反应器温度370℃,接触时间2s;第二沸腾床反应器温度260℃,接触 时 间2.25s 。丙 烯 转 化 率75%~80%,总 收 率40%,丙烯酸含量97%,平均含量93%。国内在第一反应器中采用七元组分 ( 钼-钒-磷-铁- 钴-镍-钾)的催化剂,丙烯氧化制丙烯醛;在第二反应器中采用三元组分 ( 钼- 钒-钨)的催化剂,丙烯醛氧化制丙烯酸,当丙烯∶空气∶水=1∶10∶6,接触时间5.5s,线速度0.6m/s反应温度:一段为370-390 ℃,二段为270~300℃时,以进料丙烯计,一段丙烯转化率为78.7%~87%,丙烯 醛 收 率 为 51.9%~57.2%,二 段 丙 烯 转 化 率 为79.3%~89.4%,丙烯酸收率为48.3%~49.8%,丙烯酸的空时收率为55~60kg/(m3催化剂·h) 。

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