organic chemicals FROM
R O H M &. H A A S C O M P A N Y
ACRYLIC M O N O M E R S Acrylic Esters Acrylates CH2 = CHC00R Methacrylates CH2 = CCOOR I CH,
Polymers derived from this series of acrylic and methacrylic esters vary from soft, rubber-like, filmforming materials to hard, trans parent plastics. These esters may be polymerized by bulk, suspen sion, solvent, and emulsion tech niques. They copolymerize readily
with a large number of other monomers and can contribute to the resulting copolymers: internal plasticization, better heat and light stability, improved compat ibility with other resins, better adhesion properties, greater tough ness, stability of emulsions, and solubility in alkalies. Typical uses: thermoplastic sheets and molding powders, solvent coatings, adhesives, latex paints, heatresistant elastomers, binders for explosives, water-soluble thick eners, and emulsions for textile, leather, and paper finishing. Commercially available.
Methyl Acrylate Ethyl Acrylate Butyl Acrylate 2-Ethylhexyl Acrylate Methyl Methacrylate Ethyl Methacrylate Butyl Methacrylate Hexyl Methacrylate Decyl-Octyl Methacrylate Lauryl Methacrylate Stearyl Methacrylate
Acrylic Acids Glacial acrylic acid and glacial methacrylic acid are water soluble monomers which can be poly merized to water-soluble polymers. CH2 = CHC00H Glacial Acrylic Acid CH3 ι CH2 = C - C 0 0 H Glacial Methacrylic Acid
Other
They may also be copolymerized with other monomers to obtain polymers having varying degrees of solubility in alkali or water. Typical uses: In copolymers, small quantities of these acids can: 1) provide a product which can be vulcanized with metallic oxides without the use of sulfur, or can be cross-linked with diepoxides, diamines, glycols, etc., 2) improve freeze-thaw and mechanical sta bility of emulsions, 3) improve
adhesion properties, 4) increase resistance to attack by oils, 5) provide an alkali- or ammoniasolubilizing group. Amphoteric copolymers may be produced by copolymerization with basic mon omers such as dimethylamino ethyl methacrylate. These acids also serve as intermediates for the production of special esters such as glycol diacrylates and dimethacrylates. Commercially available.
CH3O I II /H CH2 = C-COCH 2 CH 2 N X C(CH 3 ) 3 t-Butylaminoethyl Methacrylate
Dimethylaminoethyl Methacrylate (DMAEM) and t-Butylaminoethyl Methacrylate (ί-BAEM) provide means for introducing amino groups into copolymers. Both copolymerize with vinyl-type
Monomers
CH30 I II
/CH
CH2 = C-COCH 2 CH 2 N X
CH, Dimethylaminoethyl Methacrylate
continued
organic chemicals
FROM
Other M o n o m e r s (continued) monomers and undergo addition to the double bond. DMAEM is a water-soluble monomer; it can be polymerized to a water-soluble cationic polymer, or copolymerized with an acidic monomer such as m e t h a c r y l i c acid t o give a p o l y a m p h o l y t e . Copolymers of M 3 A E M exhibit good color properties. Individual reactions i n c l u d e : D M A E M — s a l t formation and quaternization; J-BAEM —typical reactions of t h e amine g r o u p via t h e active hydrogen. D M A E M and £-BAEM are suggested as intermediates for preparing anchoring agents for dyes,
p i g m e n t s , waxes, a n d moistureproofing compounds . . . dispersing a g e n t s for n o n - a q u e o u s s y s t e m s . . . antistatic agents . . . ion exchange resins . . . emulsifying a g e n t s . . . a n d cationic precipitating agents.
CH3 I
CH2 = C - C 0 N H 2 Methacrylamide Methacrylamide is a water-soluble monomer which can be polymerized to a water-soluble polyamide,
or copolymerized with other monomers to give a reactive group for cross-linking purposes. Other Rohm & Haas acrylic monomers include lauryl acrylate, decyloctyl acrylate, and sodium methacrylate. Sodium methacrylate is available commercially. DMAEM, M3AEM, methacrylamide, lauryl acrylate, and decyl-octyl acrylate are available in development quantities.
Lauryl Acrylate Decyl-Octyl Acrylate Sodium Methacrylate
t-ALKYL A M I N E S CH3 I
CH 3 -C-NH 2 I
CH3 CH3 I
t-Butylamine CH3 I
CH3-C-CH2-C-NH2 I l CH3 CH3 t-Octylamine
R' R-C-NH2
R R
' '' R " a r e alkyl groups
R' t-Nonylamine: 9-10 Carbons PRIMENE 81-R: 12-14 Carbons PRIMENE JM-T: 18-22 Carbons UH3 Un2 I / CH3-C-CH NH 2
vH2 CH3 \ / C
C H 2 - C H 2 NH 2
Menthane Diamine
t - B u t y l a m i n e , t - O c t y l a m i n e , tNonylamine, P R I M E N E 81-R, and P R I M E N E J M - T have a number of u n u s u a l properties not found in straight-chain primary amines of corresponding molecular weight range. Some are: fluid character and low viscosity over a wide temp e r a t u r e r a n g e , color s t a b i l i t y , resistance to oxidation, and excellent oil solubility. Although these amines undergo most of the reactions common to their straightchain counterparts, the attachment of t h e amino group to a tertiary carbon imparts unusual reactivity to t-alkyl amines in several reactions—e.g. formation of principally s e c o n d a r y a m i n e s in a m i n o hydrogen substitution reactions, and formation of stable aldimines ( R - N = CHR'), carbodiimides (R - N = C = N - R), and t-alkylcyanamides (R - N H - CN). T h e last t h r e e derivatives of n o r m a l primary amines are relatively unstable. Typical uses: Intermediates for bactericides, surface-active
a g e n t s , r u b b e r chemicals, antifoaming agents, flotation agents, a n t i s t a t i c a g e n t s , fungicides, pharmaceuticals, antioxidants, dyestuffs, photographic chemicals, a n d insecticides. P R I M E N E 81-R a n d P R I M E N E J M - T a r e particularly useful as oil additives. Commercially available.
Menthane Diamine, a low viscosity l i q u i d , is a p r i m a r y alicyclic d i a m i n e . Like t h e o t h e r t-alkyl a m i n e s , it h a s its amino groups a t t a c h e d to tertiary carbons and t h u s exhibits "steric-controlled" reactivity which permits aminoh y d r o g e n substitution reactions to form s e c o n d a r y a m i n e s , b u t i n h i b i t s t e r t i a r y amine format i o n . Suggested uses: c u r i n g agent for epoxy resins, and intermediate for preparing m e n t h a n e diisocyanate, polyamides, and o t h e r organic chemicals. Commercially available.
ROHM & HAAS
COMPANY
METHYLAMINES CH,NH 9
Mono — methylamine
CH3 N
Dimethylamine
QH. /
NH
CH 3 \ CH 3 — N CH 3
caffeine), analgesics not related to or derived from m o r p h i n e , dimethylaminoethanol (an intermediate for local anesthetics and antihistamines), sympathomimetic drugs (e.g. N - m e t h y l p h e n e t h y l amine or N-methylphenylpropylamine derivatives), choline chloride (poultry-feed additive), highmolecular-weight q u a t e r n a r i e s , acid-gas absorbents, and explosives. Commercially available in a q u e o u s a n d a n h y d r o u s forms.
Mono-, di-, and t r i m e t h y l a m i n e are very low-cost sources of amino nitrogen. T h e y are worth investigating as intermediates in t h e preparation of agricultural fungicides, a c c e l e r a t o r s for r u b b e r vulcanization, unsymmetrical d i m e t h y l h y d r a z i n e (for rocket propellants), surface-active agents, p-methylaminophenol (for photographic developers), 1,3-dimethylu r e a (an i n t e r m e d i a t e in t h e s y n t h e s i s of t h e o p h y l l i n e a n d
Trimethylamine
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ALKYLPHENOLS O c t y l p h e n o l is a flaked solid; nonylphenol and dodecylphenol —liquids. They undergo the normal r e a c t i o n s of t h e phenolic hydroxy group and nuclear subs t i t u t i o n of t h e benzene ring. Reactions include etherification, c o n d e n s a t i o n with a l d e h y d e s , esterification, sulfonation, halogenation, and nitration. Etherification of alkylphenols with ethylene oxide produces a variety of surface-active agents. Lubricatinga n d fuel-oil additives and vinyl s t a b i l i z e r s are o b t a i n e d from ,. sa«w> *&?& *•? *** i£&m
