Polyfunctional oxetane-based compound and production method thereof

Abstract

A group of polyfunctional oxetane-based compounds having a structure as represented by general formula (I) or a product obtained by a reaction between a compound of general formula (I) and epichlorohydrin, an ester compound, or an isocyanate compound. When these polyfunctional oxetane-based compounds are used as cation polymerizable monomers in combination with an epoxy compound, the curing speed is high, and the cured product has highly excellent hardness, flexibility, adherence, and heat resistance.

Claims

1. A cation polymerizable monomer generated by a reaction of a polyfunctional oxetane-based compound and epichlorohydrin, wherein the polyfunctional oxetane-based compound has a structure represented by formula (I): ##STR00029## wherein, R.sub.1 represents a C.sub.1-C.sub.40 linear m-valent alkyl group, a C.sub.1-C.sub.40 branched m-valent alkyl group, a C.sub.2-C.sub.20 m-valent alkenyl group, or a C.sub.6-C.sub.40 m-valent aryl group, wherein —CH.sub.2— can be substituted with an oxygen atom, —NH—, or ##STR00030## provided that two —O-'s are not directly connected, and wherein one or more hydrogen atoms in these groups can be each independently substituted with an alkyl group, a halogen, or a nitro group, R.sub.2 represents a C.sub.1-C.sub.20 linear alkylene group or a C.sub.1-C.sub.20 branched alkylene group, wherein —CH.sub.2— in the main chain can be substituted with an oxygen atom, provided that two —O-'s are not directly connected, and wherein one or more hydrogen atoms in the group can be each independently substituted with an alkyl group, a halogen, or a nitro group, R.sub.3 represents hydrogen, a halogen, a nitro group, a C.sub.1-C.sub.20 linear alkyl group, a C.sub.1-C.sub.20 branched alkyl group, a C.sub.3-C.sub.20 cycloalkyl group, a C.sub.4-C.sub.20 cycloalkylalkyl group, a C.sub.4-C.sub.20 alkylcycloalkyl group, a C.sub.2-C.sub.10 alkenyl group, or a C.sub.6-C.sub.20 aryl group, wherein one or more hydrogen atoms in these groups can be each independently substituted with an alkyl group, a halogen, and a nitro group, and m represents an integer selected from 1-8; and wherein the cation polymerizable monomer has a structure represented by formula (IV): ##STR00031## wherein R.sub.1, R.sub.2, R.sub.3, and m have the same definitions as those for formula (I).

2. The cation polymerizable monomer according to claim 1, wherein m is selected to be a numeric value of 2 or more; or when m=1, R.sub.1 is substituted by at least one oxetanyl group.

3. The cation polymerizable monomer according to claim 1, wherein R.sub.1 represents a C.sub.1-C.sub.40 linear m-valent alkyl group, a C.sub.1-C.sub.40 branched m-valent alkyl group, a C.sub.2-C.sub.10 linear m-valent alkenyl group, a C.sub.2-C.sub.10 branched m-valent alkenyl group, or a C.sub.6-C.sub.30 m-valent aryl group, wherein —CH.sub.2— can be substituted with an oxygen atom, —NH—, or ##STR00032## provided that two —O-'s are not directly connected, and wherein one or more hydrogen atoms in these groups can be each independently substituted with an alkyl group, a halogen, or a nitro group.

4. The cation polymerizable monomer according to claim 1, wherein R.sub.2 represents a C.sub.1-C.sub.10 linear alkylene group or a C.sub.1-C.sub.10 branched alkylene group, wherein —CH.sub.2— in the main chain can be substituted with an oxygen atom, provided that two —O-'s are not directly connected.

5. The cation polymerizable monomer according to claim 1, wherein R.sub.3 represents hydrogen, a C.sub.1-C.sub.10 linear alkyl group, a C.sub.1-C.sub.10 branched alkyl group, a C.sub.3-C.sub.10 cycloalkyl group, a C.sub.4-C.sub.10 cycloalkylalkyl group, a C.sub.4-C.sub.10 alkylcycloalkyl group, a C.sub.2-C.sub.8 alkenyl group, or a phenyl group.

6. The cation polymerizable monomer according to claim 1, wherein m is an integer selected from 1-6.

7. The cation polymerizable monomer according to claim 1, wherein m is an integer selected from 1-4.

8. The cation polymerizable monomer according to claim 1, wherein R.sub.1 is: a C.sub.1-C.sub.12 linear 1-to-4-valent alkyl group, a C.sub.1-C.sub.12 branched 1-to-4-valent alkyl group, a C.sub.2-C.sub.6 linear 1-to-4-valent alkenyl group, a C.sub.2-C.sub.6 branched 1-to-4-valent alkenyl group, ##STR00033## wherein * represents a bond, wherein x is an integer selected from the range of 0 to 6, y is an integer selected from the range of 0 to 6, and z is an integer selected from the range of 0 to 6.

9. The cation polymerizable monomer according to claim 1, wherein R.sub.3 represents a C.sub.1-C.sub.4 linear alkyl group, a C.sub.1-C.sub.4 branched alkyl group or a C.sub.4-C.sub.8 cycloalkylalkyl group.

10. A production method of the cation polymerizable monomer represented by formula (IV) of claim 1, wherein the production method comprises performing a reaction, under a basic condition at one or more reaction temperatures selected from 25-120° C., between a polyfunctional oxetane-based compound represented by formula (I) and epichlorohydrin to obtain the cation polymerizable monomer, wherein a reaction formula is as follows: ##STR00034##

Description

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENT(S)

(1) It is to be indicated that the described Examples and features in the Examples can be combined with each other without being conflicted. The Examples are not to be construed as limiting.

PREPARATION EXAMPLES

Example 1

(2) ##STR00012##

(3) In an example embodiment, 102 g (0.5 mol) of the raw material 1, 4 g (0.1 mol) of sodium hydroxide, and 100 g of toluene were sequentially added to a 250 ml four-neck flask mounted with a stirring apparatus, a thermometer, and a reflux condenser tube, and the temperature was increased to 80° C. with stirring. 86 g (0.5 mol) of the raw material 2 was dropped within 1.5 h, and a reaction was continued with stirring. Vapor phase tracking was performed until the content of the raw material 1 did not change anymore, and heating was stopped. The pH was adjusted to neutral, and filtration, water washing, extraction, and reduced-pressure distillation were performed to obtain 174 g of a light yellow viscous liquid.

(4) The structure of the product, i.e., compound 1, was confirmed by GC-MS and .sup.1H-NMR.

(5) MS (m/e): 376 (M);

(6) .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ0.96 (6H, m), δ1.25 (4H, s), δ2.01 (1H, d), δ3.29 (4H, s), δ3.52-3.54 (12H, m), δ3.87 (1H, m), δ4.65 (8H, s).

Example 2

(7) ##STR00013##

(8) In an example embodiment, 188 g (0.5 mol) of compound 1, 46 g (0.5 mol) of epichlorohydrin, and 20 g (0.5 mol) of sodium hydroxide were sequentially added to a 250 ml four-neck flask mounted with a stirring apparatus, a thermometer, and a reflux condenser tube, and a reaction was performed at 40° C. for 12 h. Vapor phase tracking was performed until compound 1 completely disappeared. After completion of the reaction, water washing, extraction, and reduced-pressure distillation were performed to finally obtain 198.7 g of a colorless viscous liquid

(9) The structure of the product, i.e., compound 2, was confirmed by GC-MS and .sup.1H-NMR.

(10) MS (m/e): 432 (M);

(11) .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ0.96 (6H, m), δ1.25 (4H, s), δ2.50 (2H, d), δ2.86 (1H, m), δ3.29 (4H, s), δ3.49-3.54 (15H, m), δ4.65 (8H, s).

Example 3

(12) ##STR00014##

(13) In an example embodiment, 188 g (0.5 mol) of compound 1, 33 g (0.25 mol) of dimethyl malonate, and 200 g of toluene were added to a four-neck flask mounted with a stirring apparatus, a thermometer, a rectification column, and a water trap apparatus, and moisture in the system was removed with heating reflux. After cooling down to about 60° C., 2.5 g of tetraethyl titanate was added, a reaction was performed with heating reflux, and the reflux ratio was adjusted to bring out methanol generated in the reaction. When the temperature at the top of the rectification column was increased to 110° C., the reaction was stopped, and the temperature was decreased to 70° C. 10 g of water was added with stirring for 1 h, filtration was performed while it is hot, and the filtrate was subjected to reduced-pressure distillation to obtain 197 g of a light-yellow viscous liquid.

(14) The structure of the product, i.e., compound 3, was confirmed by GC-MS and .sup.1H-NMR.

(15) MS (m/e): 821 (M);

(16) .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ0.96 (12H, m), δ1.25 (8H, m), δ3.21 (2H, s), δ3.29 (8H, s), δ3.54-3.61 (24H, m), δ4.61-4.65 (18H, m).

Example 4

(17) ##STR00015##

(18) In an example embodiment, 188 g (0.5 mol) of compound 1 and 0.1 g of dibutyltin laurate were added to a four-neck flask mounted with a stirring apparatus and a thermometer. The temperature was controlled at about 40° C., and 42 g (0.25 mol) of hexamethylene diisocyanate was dropped. After the dropping, a reaction was performed with maintaining the temperature, and the reaction was finished when the NCO value was decreased to 0.05% or less.

(19) The structure of the product, i.e., compound 4, was confirmed by GC-MS and .sup.1H-NMR.

(20) MS (m/e): 920 (M);

(21) .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ0.96 (12H, m), δ1.25-1.55 (16H, m), δ3.29 (8H, s), δ3.54-3.61 (24H, m), δ4.61-4.65 (18H, m), δ8.0 (2H, m).

Example 5

(22) ##STR00016##

(23) Compound 5 was produced with reference to the process of Example 1, and its structure was confirmed by GC-MS and .sup.1H-NMR.

(24) MS (m/e): 406 (M);

(25) .sup.1H-NMR (CDCl.sub.3, 500 MHz): δ0.96 (6H, m), δ1.25 (4H, s), δ2.01 (2H, d), δ3.29 (4H, s), δ3.52-3.54 (12H, m), δ3.87 (2H, m), δ4.65 (8H, s).

Example 6

(26) ##STR00017##

(27) Compound 6 was produced from compound 5 with reference to the process of Example 3.

(28) The structure of compound 6 was confirmed by IR.

(29) IR (KBr), ν/cm-1: 981 (s,

(30) ##STR00018##
1200 (m, C—O—C), 1720 (s, C═O), 960.7 (m, Ar—H).

Example 7

(31) Products 7-13 having structures as shown in Table 1 were synthesized by using corresponding agents with reference to the methods of Examples 1-6.

(32) TABLE-US-00001 TABLE 1 Com- pound Structure 1H-NMR/IR 7 δ 0.96 (12H, m) δ 1.25-1.46 (28H, m) δ 3.29-3.79 (16H, m) δ 4.61-4.65 (10H, m) δ 8.1 (4H, d) 8 0 δ 0.96 (15H, m) δ 1.25-1.46 (44H, m) δ 2.17 (6H, m) δ 3.37-3.61 (36H, m) δ 4.61-4.65 (15H, m) 9 δ 0.96 (12H, m) δ 1.25-1.46 (28H, m) δ 3.37-3.81 (18, m) δ 4.61-4.65 (10H, m) δ 7.04-7.52 (8H, m) δ 8.0 (2H, s) 10 δ 0.96-1.25 (20H, m) δ 2.50-2.86 (9H, m) δ 3.29-3.50 (33, m) δ 4.65 (12H, s) 11 12 13 δ 0.96 (12H, m) δ 1.25-1.55 (12H, m) δ 2.96 (4, m) δ 3.29-4.65 (22H, m) δ 6.65-8.0 (18H, m)
Test of Properties

(33) By formulating exemplary photocurable compositions, various application properties of the polyfunctional oxetane-based monomer were evaluated, including aspects of curing speed, hardness, flexibility, adherence, heat resistance, and the like.

(34) In the process of the test, TTA21 and E-51 were representative of epoxy monomers, PAG-202 was representative of a cationic photoinitiator, and the compounds a and/or b described in the background art were used as comparative polyfunctional oxetane-based monomers.

(35) ##STR00028##
1. Test of Curing Speed

(36) In an example embodiment, raw materials were formulated according to parts by mass as shown in Table 2 and then evenly mixed in a dark room, and about 1 mg of a sample was weighed and spread in an aluminum crucible. The sample was scanned and cured by using a Perkin Elmer differential scanning calorimeter (DSC8000) equipped with an ultraviolet light source of a mercury arc lamp (OmniCure-S2000).

(37) The time when the maximal curing heat release was induced by UV and the time required for achieving 90% of UV curing heat release were recorded. A shorter time when the peak was reached and a shorter time when 90% conversion was achieved were indications of good curing properties. Test results are summarized in Table 2.

(38) TABLE-US-00002 TABLE 2 1# 2# 3# 4# 5# 6# 7# 8# 9# 10# PAG202 2 2 2 2 2 2 2 2 2 2 TTA21 49 49 49 49 49 — — — — — E-51 — — — — — 49 49 49 49 49 Compound 2 49 — — — — 49 — — — — Compound 3 — 49 — — — — 49 — — — Compound 8 — 49 — — — — 49 — — Compound 10 — — — 49 — — — — 49 — Compound b — — — — 49 — — — — 49 Time when the peak 0.12 0.08 0.10 0.09 0.16 0.38 0.20 0.33 0.25 0.68 is reached/min Time when 90% is 1.15 0.96 1.05 1.04 1.32 3.25 2.42 3.06 2.90 4.58 achieved/min

(39) As can be seen from Table 2, after the disclosed polyfunctional oxetane-based monomer was used in combination with an epoxy monomer in a cationic photocuring system, it had a high curing speed and was superior to an existing compound having the same type of structure, i.e., compound b.

(40) 2. Test of Properties after Film-Forming by Curing

(41) The polyfunctional oxetane-based monomers of this disclosed or compounds a and b each was mixed with an epoxy monomer TTA21 at a mass ratio of 1:1, and 2% of an initiator PAG-202 was further added. After evenly stirring and mixing in a dark room, formulations were coated onto a sand paper-polished tin-plated steel sheet substrates with 25# wire bar to obtain coating layers having a thickness of about 25 μm. The formulations were then placed in a track type exposure machine (RW-UV.70201) and completely exposed 10 times, wherein each exposure was 80 mj/cm2. The test was then performed after standing for 24 h.

(42) (1) Test of Hardness

(43) Cured films were tested under conditions of a temperature of 23° C. and a relative humidity of 50%. The evaluation method for pencil hardness specified in GB/T 6739-2006 was used as a standard. A pencil was inserted into a test instrument, fixed with a clip, and maintained to be horizontal. The tip of the pencil was placed on the surface of a paint film, and was pushed by a distance of at least 7 mm at a speed of 1 mm/s toward a direction departing from yourself. If no scratch occurred, an experiment was repeated in an untested area by replacing with a pencil having a higher hardness, until a scratch having a length of at least 3 mm occurred. The hardness of the coating layer was represented by the hardness of hardest pencil which did not allow the occurrence of scratch on the coating layer.

(44) (2) Test of Flexibility

(45) Cured films were tested under conditions of a temperature of 23° C. and a relative humidity of 70%. On the basis of the test method of the flexibility of paint films in GB/T1731-93, the outside of a tin-plated steel plate coated with a cured coating layer was sequentially wound onto 10-, 5-, 4-, 3-, 2-, and 1-millimeter rod shafts along the length direction and bent for 2-3 s. By observing with a magnifier, the flexibility of the ultraviolet photocured coating layer was represented by the diameter of the rod shaft having the smallest damage of the coating layer.

(46) (3) Test of Adherence

(47) Cured films were tested under conditions of a temperature of 23° C. and a relative humidity of 50%. The evaluation method for paint film crosscut specified in GB/T 9286-1998 was used as a standard. A coating film was cut into one hundred grids. The tip of the cutter was required to scratch the substrate and to be sharp, and the angle formed between the tip of the cutter and the coating film was 45 degrees. Paint scraps were brushed off with a soft brush, a 3M adhesive tape was stuck onto the one hundred grids, and a force was applied to allow the adhesive tape to be firmly stuck onto the surface of the coating film and the crosscut parts. Within 2 min, one end of the 3M adhesive tape was held firmly to form an angle of 60 degrees, and the adhesive tape was steadily peeled off in 1 second. The evaluation was performed according to the criteria described below.

(48) Grade 0: Cut edges were completely smooth and nothing fell off;

(49) Grade 1: A few parts of the coating layer fell off at the intersections of cuts, but the influenced crosscut area could not be significantly greater than 5%;

(50) Grade 2: Parts of the coating layer fell off at the intersections of cuts and/or along the edges of cuts, and the influenced crosscut area was significantly greater than 5% but could not be significantly greater than 15%;

(51) Grade 3: The coating layer fell off partly or completely in the form of large fragments along the cut edges and/or fell off partly or completely on different parts of the grids, and the influenced crosscut area was significantly greater than 15% but could not be significantly greater than 35%;

(52) Grade 4: The coating layer fell off in the form of large fragments along the cut edges and/or some grids fell off partly or completely, and the influenced crosscut area was significantly greater than 35% but could not be significantly greater than 65%;

(53) Grade 5: The degree of falling-off exceeded Grade 4.

(54) (4) Test of Glass Transition Temperature

(55) A test was performed on the cured film by using a differential scanning calorimeter (PE DSC8000) under a test condition as follows: under a nitrogen atmosphere, the temperature was increased from −20° C. to 200° C. at a rate of 10° C./min and maintained at 200° C. for 1 min, then decreased from 200° C. to −20° C. at a rate of 10° C./min and maintained at −20° C. for 1 min, and increased from −20° C. to 200° C. at a rate of 10° C./min, so that the glass transition temperature Tg (° C.) was measured.

(56) (5) Test of Thermal Decomposition Temperature

(57) A thermogravimetric analysis was performed on the cured film by using a thermogravimetric analyzer (PE STA6000). The temperature of a part, where a tangent line of a part where the weight was not decreased or was gradually decreased and a tangent line of an inflection point where the weight was rapidly decreased were intersected, was taken as a thermal decomposition temperature T (° C.). The evaluation was performed according to the criteria described below.

(58) A thermal decomposition temperature T (° C.) at 300 or more was denoted by: Δ;

(59) A thermal decomposition temperature T (° C.) at 250-300 or more was denoted by: ∘; and

(60) A thermal decomposition temperature T (° C.) at 250 or less was denoted by: x.

(61) Evaluation results were summarized in Table 3.

(62) TABLE-US-00003 TABLE 3 Tg Heat Compound Hardness Flexibility Adherence (° C.) Resistance Disclosed Compound 3 4H 1 Grade 0 96 ◯ Compounds Compound 6 4H 1 Grade 0 128 Δ Compound 8 4H 2 Grade 0 115 Δ Compound 10 4H 2 Grade 0 109 Δ Compound 12 4H 1 Grade 0 132 Δ Compound 13 4H 3 Grade 0 105 Δ Comparative Compound a 2H 3 Grade 1 75 X Example Compound b 4H 5 Grade 1 84 ◯

(63) As can be seen from Table 3, compared to compound a, the advantages in terms of hardness, flexibility, adherence, and heat resistance were highly significant after the disclosed polyfunctional oxetane-based compounds were used in a cationic photocuring system; while compared to compound b having a more similar structure, these compounds also exhibited better properties in terms of flexibility, adherence, and heat resistance and had more excellent overall properties.

(64) In summary, the polyfunctional oxetane-based compound of the disclosed compound have excellent application properties in a cationic photocuring system, good adjustability of structures and properties, and can satisfy various application requirements.

(65) Those described above are merely preferred Examples and are not intended to be limiting. With respect to the person skilled in the art, there may be various modifications and variations of this invention. All of modifications, equivalent replacements, improvements, and the like, which are within the spirit and the principle of this invention, should be encompassed in the scope protected by this invention.

(66) While particular elements, embodiments and applications of the present invention have been shown and described, it will be understood, that the invention is not limited thereto since modifications can be made by those skilled in the art without departing from the scope of the present disclosure, particularly in light of the foregoing teachings.