CN105153223A - SLA type phosphorus-containing acrylic acid ester prepolymer for 3D printing and preparation method thereof - Google Patents
SLA type phosphorus-containing acrylic acid ester prepolymer for 3D printing and preparation method thereof Download PDFInfo
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- CN105153223A CN105153223A CN201510464510.9A CN201510464510A CN105153223A CN 105153223 A CN105153223 A CN 105153223A CN 201510464510 A CN201510464510 A CN 201510464510A CN 105153223 A CN105153223 A CN 105153223A
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Abstract
The invention discloses a SLA type phosphorus-containing acrylic acid ester prepolymer for 3D printing and a preparation method thereof, and the preparation method comprises the following steps: mixing 2-methy-2,5-dioxo-1,2-oxaphospholane OP and hydroxyl acrylate compounds according to a mol ratio which is 1:1, adding a catalyst and a polymerization inhibitor, carrying out a reaction at 110-130 DEG C for 5-6 hours, and obtaining the phosphorus-containing acrylic acid ester prepolymer, and the structure general formula of the phosphorus-containing acrylic acid ester prepolymer is shown in the figure, wherein R1 = H2C = CH- or R2 = -CH2-CH2- or -CH2-CH2-CH2-CH2-.
Description
Technical field
The present invention relates to 3D printing technique field, refer to a kind of SLA type phosphoric acrylic ester prepolymer for 3D printing and preparation method thereof particularly.
Background technology
Photocuring solid forming adopts stereosopic printing (StereoLithographyApparatus, SLA) a kind of technique of principle, also be occur the earliest, the most ripe and most widely used rapid prototyping technology of technology, released in the later stage eighties 20th century by 3DSystems company of the U.S..The manufacturing process of SLA fills with liquid photosensitive resin in resin liquid bath, make its fast setting under the irradiation of laser beam, when forming process starts, liftable worktable is in the height of liquid level next cross section thickness, the laser beam after focusing, under control of the computer, according to the requirement of cross section profile, scan along liquid level, make by the resin solidification of scanning area, thus obtain the plastic tab of this cross section profile.Then, worktable declines the height of one deck thin slice, and the plastic tab solidified is just by liquid resin institute top cover that one deck is new, to carry out second layer laser scanning solidification, one deck of new solidification securely withered knot on front one deck, so repeats endlessly, until whole product shaping is complete.Because SLA technical cure speed is fast, production efficiency is high and the advantage such as Suitable commercial production line balance, SLA photosensitive resin is applied in quick forming fabri-cation industry more and more in a large number.
Photosensitive resin at present for SLA technology consists of the following components substantially: matrix resin oligopolymer, light trigger and reactive thinner, oligopolymer has effects such as accelerating solidification, minimizing contraction, adjustment viscosity in photosensitive resin, be the main component of photosensitive resin, decide the mechanical property printing goods to a certain extent.Conventional oligopolymer can be divided into acrylic resin and the large class of epoxy resin two, corresponds respectively to radically curing system and Cationic curing systems.But the acrylic acid or the like oligopolymer overwhelming majority of photosensitive resin is inflammable in existing SLA technology, and along with the fast development of SLA technology and large-scale application, this shortcoming will limit its range of application, hinders the development of whole industry.If add the fire retardants such as phosphorus oxychloride in SLA photopolymer system, though can solve fire-retardant problem, phosphorus oxychloride has high toxicity, can decomposite HCl, to environment, and there is some problems as the consistency of inorganics and SLA photosensitive resin.Therefore, from prepolymer self, develop the acrylic acid or the like oligopolymer had in the SLA photosensitive resin of flame retardant properties and have great importance.
Summary of the invention
Object of the present invention is exactly the deficiency that will solve above-mentioned background technology, provides a kind of SLA type phosphoric acrylic ester prepolymer for 3D printing and synthetic method thereof.
Technical scheme of the present invention is: a kind of phosphoric acrylic ester prepolymer, and its general structure is:
Wherein,
in one.
The present invention also provides a kind of preparation method of above-mentioned phosphoric acrylic ester prepolymer, it is characterized in that, step is: by 2-methyl-2,5-dioxy-1,2-oxygen phospholane (being called for short OP) mixes with the ratio of mol ratio 1:1 with hydroxyl acrylic ester compound, add catalyzer and stopper reacts 5-6h at 110-130 DEG C, obtain phosphoric acrylic ester prepolymer;
Described hydroxyl acrylic ester compound is the one in Hydroxyethyl acrylate, propenoic acid beta-hydroxy propyl ester, hy-droxybutyl, hydroxyethyl methylacrylate, methacrylic acid β-hydroxypropyl acrylate.
Preferably, described stopper is the one or more combination in Resorcinol, MEHQ, para benzoquinone, N-phenyl-2-naphthylamine, p-ten.-butylcatechol.
Further, described stopper consumption be 2-methyl-2,5-dioxy-1,2-oxygen phospholane OP and hydroxyl acrylic ester compound quality and 0.1-5.0%.
Preferably, described catalyzer is the one or more combination in storng-acid cation exchange resin PK208LH, PK212LH, RCP106M, D001, NKC-9.PK208LH, PK212LH, RCP106M are the storng-acid cation exchange resin that Mitsubishi Chemical produces, and D001, NKC-9 are the storng-acid cation exchange resin that resin processing plant of University Of Tianjin produces.
Further, described catalyst levels be 2-methyl-2,5-dioxy-1,2-oxygen phospholane OP and hydroxyl acrylic ester compound quality and 5-8%.
In the present invention, the reaction process of 2-methyl-2,5-dioxy-1,2-oxygen phospholane OP and hydroxyl acrylic ester compound is:
Wherein, hydroxyl acrylic ester compound general formula is
in one.
Beneficial effect of the present invention is:
1. by 2-methyl-2,5-dioxy-1,2-oxygen phospholane OP and hydroxyl acrylic ester compound synthesize phosphoric acrylic ester prepolymer, phosphorus is introduced in acrylate, make its prepolymer have good flame retardant properties under the condition of Halogen, thus minimizing does not even adopt any other additional type fire retardant.
2. prepolymer itself has flame retarding construction, contaminate environment can not be formed in use procedure after hardening or impair the material of person health, safety and environmental protection, avoids when the flame retardant resistance in order to photosensitive resin adds phosphorous inorganics, damages the person.
Both containing phosphorus in 3.OP, there is again the structure of acid anhydrides, can well be combined with hydroxyl acrylic ester compound, existing oil-soluble ester structure in the prepolymer of generation, not only there is again water miscible hydroxyl structure, make prepolymer may be used for oil soluble system but also may be used for aqueous solution systems.
Accompanying drawing explanation
Fig. 1 is the FTIR collection of illustrative plates of phosphorous Hydroxyethyl acrylate prepolymer
Fig. 2 is the NMR-H of phosphorous Hydroxyethyl acrylate prepolymer
1collection of illustrative plates
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
Get 13.40g (0.1mol) OP and 11.60g (0.1mol) Hydroxyethyl acrylate in there-necked flask, add 2.00g catalyzer storng-acid cation exchange resin PK208LH (catalyst quality be OP and Hydroxyethyl acrylate quality and 8%) and 0.0250g hydroquinone of polymerization retarder (stopper quality be OP and Hydroxyethyl acrylate quality and 0.1%), at 110 DEG C, stopped reaction after reaction 5h.Product phosphoric acrylic ester prepolymer in system is separated: add 100mL ethyl acetate, continue to stir 30min, be reduced to behind room until system temperature, filter with cloth funnel and PK208LH resin cation (R.C.) is separated with reaction solution (isolated PK208LH resin is soaked and washes away phosphoric acrylic ester prepolymer in ethanol to reuse), filtrate is added in the pyriform funnel of 250mL, add saturated aqueous common salt 50ML two-phase acutely to mix and wash away stopper and unreacted OP, saturated common salt water layer proportion is larger in lower floor, lower floor is released stand-by, the each 50mL of saturated aqueous common salt washes three times continuously, by ethyl acetate 200mL extracting twice after lower floor's salt solution merges, after the oil phase merging anhydrous sodium sulfate drying that ethyl acetate phase extract and upper strata obtain, underpressure distillation removing ethyl acetate and Hydroxyethyl acrylate obtain phosphoric acrylic ester prepolymer 18g, and molar yield is 72%.
Embodiment 2
Get 13.40g (0.1mol) OP and 13.00g (0.1mol) senecioate-hydroxypropyl acrylate in there-necked flask, add 2.00g catalyzer storng-acid cation exchange resin PK208LH (catalyst quality be OP and senecioate-hydroxypropyl acrylate quality and 7.58%) and 0.0264g hydroquinone of polymerization retarder (stopper quality be OP and senecioate-hydroxypropyl acrylate quality and 0.1%), at 110 DEG C, reaction 5h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), and molar yield is 68%.
Embodiment 3
Get 13.40g (0.1mol) OP and 14.40g (0.1mol) vinylformic acid-4-hydroxy butyl ester in there-necked flask, add 2.00g catalyzer storng-acid cation exchange resin PK208LH (catalyst quality be OP and vinylformic acid-4-hydroxy butyl ester quality and 7.18%) and 0.0278g hydroquinone of polymerization retarder (stopper quality be OP and vinylformic acid-4-hydroxy butyl ester quality and 0.1%), at 110 DEG C, reaction 5h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), and molar yield is 79%.
Embodiment 4
Get 13.40g (0.1mol) OP and 13g (0.1mol) hydroxyethyl methylacrylate in there-necked flask, add 2.11g catalyzer storng-acid cation exchange resin PK212LH (catalyst quality be OP and hydroxyethyl methylacrylate quality and 8%) and 0.132g stopper MEHQ (stopper quality be OP and hydroxyethyl methylacrylate quality and 0.5%), at 110 DEG C, reaction 5h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), and molar yield is 65%.
Embodiment 5
Get 13.40g (0.1mol) OP and 14.40g (0.1mol) methacrylic acid-β-hydroxypropyl acrylate in there-necked flask, add 1.39g catalyzer storng-acid cation exchange resin PK212LH (catalyst quality be OP and methacrylic acid-β-hydroxypropyl acrylate quality and 5%) and 0.278g stopper para benzoquinone (stopper quality be OP and methacrylic acid-β-hydroxypropyl acrylate quality and 1%), at 120 DEG C, reaction 6h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), and molar yield is 70%.
Embodiment 6
Get 13.40g (0.1mol) OP and 11.6g (0.1mol) Hydroxyethyl acrylate in there-necked flask, add 1.5g catalyzer storng-acid cation exchange resin RCP106M (catalyst quality be OP and Hydroxyethyl acrylate quality and 6%) and 0.5g stopper N-phenyl-2-naphthylamine (stopper quality be OP and Hydroxyethyl acrylate quality and 2%), at 120 DEG C, reaction 5.5h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), and molar yield is 75%.
Embodiment 7
Get 13.40g (0.1mol) OP and 13 (0.1mol) g senecioate-hydroxypropyl acrylate in there-necked flask, add 1.85g catalyzer storng-acid cation exchange resin D001 (catalyst quality be OP and senecioate-hydroxypropyl acrylate quality and 7%) and 1.32g stopper p-ten.-butylcatechol (stopper quality be OP and senecioate-hydroxypropyl acrylate quality and 5%), at 110 DEG C, reaction 5.5h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), and molar yield is 78%.
Embodiment 8
Get 13.40g (0.1mol) OP and 14.4g (0.1mol) vinylformic acid-4-hydroxy butyl ester in there-necked flask, add 2.22g catalyzer storng-acid cation exchange resin D001 (catalyst quality be OP and vinylformic acid-4-hydroxy butyl ester quality and 8%) and 1.112g stopper MEHQ (stopper quality be OP and vinylformic acid-4-hydroxy butyl ester quality and 4%), at 120 DEG C, reaction 6h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), and molar yield is 80%.
Embodiment 9
Get 13.40g (0.1mol) OP and 13g (0.1mol) hydroxyethyl methylacrylate in there-necked flask, add 1.45g catalyzer (catalyst quality be OP and hydroxyethyl methylacrylate quality and 5.5%), catalyzer by storng-acid cation exchange resin PK212LH and NKC-9 in mass ratio 1:1 form, add 0.66g stopper (stopper quality be OP and hydroxyethyl methylacrylate quality and 2.5%), stopper is para benzoquinone and N-phenyl-2-naphthylamine 1:1 composition in mass ratio, at 130 DEG C, reaction 5h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), molar yield is 74%.
Embodiment 10
Get 13.40g (0.1mol) OP and 14.4g (0.1mol) methacrylic acid-β-hydroxypropyl acrylate in there-necked flask, add 1.81g catalyzer (catalyst quality be OP and methacrylic acid-β-hydroxypropyl acrylate quality and 6.5%), catalyzer is by storng-acid cation exchange resin PK212LH, RCP106M, D001, NKC-9 is 1:1:1:1 composition in mass ratio, add 1.39g stopper (stopper quality be OP and methacrylic acid-β-hydroxypropyl acrylate quality and 5%), stopper is dihydroxy-benzene, para benzoquinone and MEHQ be 1:1:1 composition in mass ratio, at 130 DEG C, reaction 5h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), molar yield is 69%.
Structured testing:
In embodiment 1, the infared spectrum of phosphorous Hydroxyethyl acrylate prepolymer, Hydroxyethyl acrylate and OP is shown in Fig. 1, obtained phosphorous Hydroxyethyl acrylate prepolymer in embodiment 1
1fig. 2 is shown in by H-NMR (DMSO-D6) collection of illustrative plates.
From Fig. 1 infared spectrum, b curve can be found out at 1709cm
-1place is C=O stretching vibration, at 1637cm
-1place is the charateristic avsorption band of C=C, at 1130cm
-1place is the charateristic avsorption band of P=O, at 979cm
-1corresponding is C-P stretching vibration absorption peak, and the characteristic group that there is acrylic acid groups and phosphorus is described in target molecule.In addition, contrast b spectrogram and a, c spectrogram can find out that the charateristic avsorption bands such as C=O, C=C, P=O, C-P all produce red shift, illustrate that Hydroxyethyl acrylate and OP react.From Fig. 2
1h-NMR (DMSO-D6) pattern analysis results: δ/ppm:1.28-1.44 (3H ,-CH
3, a), 1.76-2.43 (4H ,-CH
2-, c, d), 3.59-4.29 (4H ,-CH
2-, e, f), 5.93-6.39 (3H ,-CH=CH
2, g, h, i).From FT-IR analyze and
1h-NMR analyzes can prove that synthetic product is phosphorous Hydroxyethyl acrylate.
Claims (6)
1. a phosphoric acrylic ester prepolymer, its general structure is as follows:
Wherein,
R
1=H
2c=CH-or
R
2=-CH
2cH
2-,
or-CH
2-CH
2-CH
2-CH
2-in one.
2. the preparation method of a phosphoric acrylic ester prepolymer as claimed in claim 1, it is characterized in that, step is: by 2-methyl-2,5-dioxy-1,2-oxygen phospholane OP mixes with the ratio of mol ratio 1:1 with hydroxyl acrylic ester compound, add catalyzer and stopper reacts 5-6h at 110-130 DEG C, obtain phosphoric acrylic ester prepolymer;
Described hydroxyl acrylic ester compound is the one in Hydroxyethyl acrylate, senecioate-hydroxypropyl acrylate, vinylformic acid-4-hydroxybutyl, hydroxyethyl methylacrylate, methacrylic acid-β-hydroxypropyl acrylate.
3. preparation method as claimed in claim 2, it is characterized in that, described stopper is the one or more combination in Resorcinol, MEHQ, para benzoquinone, N-phenyl-2-naphthylamine, p-ten.-butylcatechol.
4. as claimed in claim 2 or claim 3 preparation method, is characterized in that, described stopper consumption be 2-methyl-2,5-dioxy-1,2-oxygen phospholane OP and hydroxyl acrylic ester compound quality and 0.1-5.0%.
5. preparation method as claimed in claim 2, it is characterized in that, described catalyzer is the one or more combination in storng-acid cation exchange resin PK208LH, PK212LH, RCP106M, D001, NKC-9 resin.
6. the preparation method as described in claim 2 or 5, is characterized in that, described catalyst levels be 2-methyl-2,5-dioxy-1,2-oxygen phospholane OP and hydroxyl acrylic ester compound quality and 5-8%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09124668A (en) * | 1995-10-25 | 1997-05-13 | Sanyo Chem Ind Ltd | Phosphorus-containing ethylenic unsaturated monomer and flame-retardant resin using the same |
| US20010014706A1 (en) * | 2000-02-09 | 2001-08-16 | Schill & Seilacher (Gmbh & Co.) | Latent combination compounds and latent ammonium salts comprising epoxide resin curing agents and flame-protection agents as well as epoxide resin systems and products prepared from them |
| CN1756969A (en) * | 2003-03-05 | 2006-04-05 | 富士胶片株式会社 | High refractive index layer production process of curable coating composition, antireflection film, polarizing plate and image display device using thereof |
| US20070221893A1 (en) * | 2006-03-21 | 2007-09-27 | Clariant International Ltd. | Phosphorus-containing mixtures, a process for their preparation and their use |
| US20070225414A1 (en) * | 2006-03-21 | 2007-09-27 | Clariant International Ltd | Phosphorus-containing mixtures, a process for their preparation and their use |
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2015
- 2015-07-31 CN CN201510464510.9A patent/CN105153223B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09124668A (en) * | 1995-10-25 | 1997-05-13 | Sanyo Chem Ind Ltd | Phosphorus-containing ethylenic unsaturated monomer and flame-retardant resin using the same |
| US20010014706A1 (en) * | 2000-02-09 | 2001-08-16 | Schill & Seilacher (Gmbh & Co.) | Latent combination compounds and latent ammonium salts comprising epoxide resin curing agents and flame-protection agents as well as epoxide resin systems and products prepared from them |
| CN1756969A (en) * | 2003-03-05 | 2006-04-05 | 富士胶片株式会社 | High refractive index layer production process of curable coating composition, antireflection film, polarizing plate and image display device using thereof |
| US20070221893A1 (en) * | 2006-03-21 | 2007-09-27 | Clariant International Ltd. | Phosphorus-containing mixtures, a process for their preparation and their use |
| US20070225414A1 (en) * | 2006-03-21 | 2007-09-27 | Clariant International Ltd | Phosphorus-containing mixtures, a process for their preparation and their use |
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