CN102140300B - Quick-drying unsaturated polyester resin marking coating and preparation method thereof - Google Patents
Quick-drying unsaturated polyester resin marking coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a quick-drying unsaturated polyester resin marking coating and a preparation method thereof. The marking coating is prepared from the following raw materials in percentage by weight: 30-50 percent of modified unsaturated polyester resin, 5-12 percent of titanium pigment, 40-50 percent of quartz powder, 2-5 percent of white carbon black, 1-3 percent of kaoline, 0.5-2 percent of titanate coupling agent, 1-3 percent of cobalt naphthenate and 0.5-1.5 percent of methyl ethyl ketone peroxide, wherein the modified unsaturated polyester resin is obtained by the steps of preparing unsaturated polyester resin by performing esterification and condensation on monoester maleate end-capped by dicyclopentadiene and propylene glycol, and adding a methyl methacrylate monomer diluent into the unsaturated polyester resin. The preparation method comprises the following step of: ultrasonically mixing the components with the amount in a formula for 3-7 minutes to obtain a quick-drying unsaturated polyester resin marking coating. During construction, the cobalt naphthenate and the methyl ethyl ketone peroxide are added for curing to form an unsaturated polyester resin marked line, which has the wear resistance superior to that required by a national standard.
Description
Technical field:
The present invention relates to a kind of coating, relate in particular to a kind of quick-dry type unsaturated polyester resin road traffic mark-line coating and preparation method thereof.
Background technology:
Road mark paint is a kind of coating that is coated on the road surface indication traffic, and at present, common on the market have a three major types road mark paint, mainly comprises normal temperature solvent-borne type, hot-melting type and two component road mark paints etc.
The normal temperature solvent based coating is to be made of filmogen and two parts of organic solvent.Spray coating by spray gun during construction, solvent volatilizees naturally, forms the graticule film.Filmogen adopts chlorinated rubber, Resins, epoxy etc. usually.Advantage is: it is simple and easy to construct, and time of drying is shorter, can be open to traffic in about 3～4 hours.At present, be extensive use of at China's urban road and Ordinary Rd.Shortcoming is: contaminate environment.Solvent adopts aromatic hydrocarbons mostly, and toxicity is big, and organic solvent emission amount during construction (VOC value, down together) is very high, and is extremely harmful to human body and environment; The maintenance cost height.The graticule film is very thin, and (0.2mm～0.3mm), not wear-resisting, the frequent overcoating of needs is constructed.
Hot-melting type coating is with natural resin or petroleum resin blended solid filler, through making after fusion, stirring, the cooling.Be powder agglomates shape material at normal temperatures.Through heat, fusion is the liquid of flow state during construction, sprays or be coated on the road surface, becomes the solid graticule film that is bonded on the road surface after the cooling.Advantage is: the graticule film is short time of drying, is about 5～10 minutes, can be open to traffic fast.The graticule film thickness is moderate, is about 1.5mm, indicates attractive in appearancely, lasting, and nighttime visibility is good.At present, it is mainly in China's highway and motorway use more than 2 grades.Shortcoming is: energy consumption is big.During construction, coating need be heated to 180 ℃～220 ℃, and fusion is the construction of liquid back; The overcoating difficulty is big.After the old hot melt type gage mark breakage, recoat need be carried out in the road surface, because it solidifies fast, to construction evenness of road surface requirement height, must even or polish old graticule earlier out, and workload is big, and destroys pavement structure easily.
Dual-component coating is to be made of the component A that adds initiator and the component B that adds promotor, forms the graticule film by crosslinking reaction.Under the normal temperature, A and two component sprays of B are mixed on the road surface, resin generation chemical reaction, crosslinking curing form weather resistance graticule film.Two component gage mark coatings have following four advantages:
1) overwhelming majority of resin in the coating has been participated in cross-linking and curing reaction, and the VOC value is extremely low.
2) the graticule film of crosslinking reaction formation is high molecular polymer, and is tougher, and because the graticule film is thicker relatively, more wear-resisting.
3) cold spraying construction under the normal temperature need not heating.
4) two component liquid coatings have levelling property, can form smooth graticule film on the road surface naturally.Shortcoming is: 1) use cost height.At present, the high performance acrylic resin of general employing is produced two component road mark paints in the world.Because the acrylic resin unstable product quality of domestic production, gage mark coating producer is in order to ensure quality product, usually DEGAROUTE (Degussa) acrylic resin of buying Germany for the production of, about 3～40,000 yuan/ton, directly cause domestic dual-component coating to hold at high price.Because domestic general employing imported raw material allotment
(1), cause the cost height, be difficult to promote.
2) not wear-resisting.(average 30mg) is similar with hot-melting type coating for the wear resistance index of bi-component acrylic type gage mark coating, but because its graticule film thickness is generally 1mm, and the graticule film thickness of hot-melting type coating is at least 1.5mm, and this just causes it can be ground off quickly on the road surface.
Summary of the invention:
The object of the present invention is to provide quick-dry type unsaturated polyester resin gage mark coating that a kind of cost is lower, wear resistance is good and preparation method thereof.
1, the objective of the invention is to be achieved through the following technical solutions: a kind of quick-dry type unsaturated polyester resin gage mark coating, made by following raw material by weight percentage:
Modified unsaturated polyester resin 30～50%
Titanium dioxide 5～12%
Silica powder 40～50%
White carbon black 2～5%
Kaolin 1～3%
Titanate coupling agent 0.5～2%
Cobalt naphthenate 1～3%
Methylethyl ketone peroxide 0.5～1.5%
Above-mentioned each component summation by weight percentage is 100%.
Screening formulation is as follows:
Modified unsaturated polyester resin 43.2%
Titanium dioxide 6.34%
Fineness is 350～400 purpose silica powders 42.24%
White carbon black 2.64%
Kaolin 1.58%
Titanate coupling agent 1%
Cobalt naphthenate 2%
Methylethyl ketone peroxide 1%
Described modified unsaturated polyester resin can adopt the product of commercially available prod or existing bibliographical information, as Chinese patent application CN96119856.7, CN200510026882.X and CN200910058017.1, the present invention preferably adopts the maleic acid monoesters (DHCM) and the unsaturated polyester resin that propylene glycol (PG) esterification condensation obtains of dicyclopentadiene (DCPD) end-blocking, adds the methyl methacrylate monomer thinner then and makes.
2, the preparation method of quick-dry type unsaturated polyester resin gage mark coating of the present invention, it is characterized in that the modified unsaturated polyester resin of formula ratio, titanium dioxide, silica powder, white carbon black, kaolin, titanate coupling agent dropped in the ultrasonic wave mixing tank and carry out ultrasonic mixing 3～7 minutes, namely get quick-dry type unsaturated polyester resin gage mark coating goods, during construction, add cobalt naphthenate and methylethyl ketone peroxide respectively and solidify to form the unsaturated polyester resin graticule.
Concrete preparation method is: at first, use dicyclopentadiene (DCPD) as the end-capping reagent of cis-butenedioic anhydride (MA), prepare DCPD-maleic acid monoesters (DHCM); Its two, with DHCM: the mol ratio of propylene glycol (PG)=2: 1, the polyester (UP) that synthetic two ends are sealed by DCPD; Its three, dilute UP with methyl methacrylate, obtain novel UPR; They are four years old, GB requirement according to gage mark coating, take the lead in this UPR is applied in two component road mark paints, adopt the ultra-sonic oscillation blending means, various filler additions are adjusted in screening, reduce dope viscosity with the corrdination type titanate coupling agent, make the outstanding quick-dry type UPR gage mark coating of over-all properties.
Preferred preparation method is: 1) the MA hydrolysis generates maleic acid; 2) DCPD with the carboxyl generation addition reaction of maleic acid, generates DHCM under 110～140 ℃ of conditions; 3) the esterifying polycondensation reaction takes place as monobasic unsaturated acid and PG in DHCM under esterifying catalyst, obtains the UP of DCPD end-blocking; 4) UP of DCPD end-blocking with the methyl methacrylate dilution, obtains the unsaturated polyester resin of DCPD modification; 5) modified unsaturated polyester resin that the step 4) of formula ratio is obtained drops into titanium dioxide, silica powder, white carbon black, kaolin, titanate coupling agent and carries out ultrasonic mixing 3～7 minutes in the ultrasonic wave mixing tank, namely gets quick-dry type unsaturated polyester resin gage mark coating goods.
Above-mentioned steps 3) DHCM as monobasic unsaturated acid and PG under the methanesulfonic acid catalyzed agent, catalyst consumption is counted 0.01～0.02wt% with reaction-ure mixture and is constantly stirred under nitrogen protection under normal pressure, progressively heats up, utilize fractional column, constantly separate and the discharge reaction water, carry out the esterifying polycondensation reaction gradually, slowly be warmed up to 200 ℃, when the reactant acid number is reduced to 30～40mgKOH/gUP, stopped reaction begins cooling; Treat that temperature is reduced to 125 ℃, adding in its massfraction of reaction product is the hydroquinone of polymerization retarder of 0.015～0.025wt%, stirs the UP that obtains the DCPD end-blocking; Continue cooling, when temperature is 90～110 ℃, add methyl methacrylate monomer, fully stir and cool off, obtain the UPR of the DCPD modification of brown yellow transparent liquid.The above-mentioned methyl methacrylate monomer that adds accounts for 30～40wt% of the UPR amount of modification.
Advantage of the present invention is: the present invention optimizes the temperature and time of DCPD addition, has obtained optimum reaction condition.Experimental result shows: the gage mark coating that adopts brand-new combined preparation such as above-mentioned UPR kind, auxiliary agent and working method, because UPR has the advantage of acroleic acid resin and two kinds of resins of unsaturated polyester concurrently, the air-drying property gage mark coating of preparing and the contrast of present propenoic acid paint, its wear resistance index is 18mg, be better than the 30mg mean value of propenoic acid paint, more be better than the requirement of GB 40mg.All other indexs meet the road mark paint GB and require (coating GB see Table 1, table 2), and cost is low, has a good application prospect.
Embodiment:
The present invention is described in detail below in conjunction with embodiment:
1.2 the present invention studies imagination and research thinking
Document, patent show that in the resin that China produces, output is big, the product of cross-linkable solidifying has two big classes usually: a class is acrylic resin, and another kind of is UPR
(2)In theory, they can be used to two component gage mark coatings.In actual applications, acrylic resin is owing to water-fast, alkaline-resisting, UV resistant are shone ability good (good weatherability) and preferentially be used for pair component gage mark coatings.
The main products of the high-performance acrylic acid of China's production at present resin also needs import, domestic general employing imported raw material allotment
(1), make that the two component gage mark coating costs of production are too high, be difficult to apply.
Meanwhile, China but is the big country that produces UPR, and product category is many, and technology is quite ripe
(3-4), and big, cheap for the manufacture of the industrial chemicals output of UPR, production cost is low.
Therefore, if can through innovation, produce a kind of better UPR of low cost, weathering resistance and wear resistance that is exclusively used in two component gage mark coatings by existing UPR technology, will improve the cost performance of gage mark coating greatly, promote the market development and popularization.
Through consulting industry standard, pavement marking paint must satisfy the technical indicator of table 1, in order to develop high-quality gage mark coating, also should satisfy the technical indicator of table 2.
Table 1 transportation industry standard JT/T 280-2004 " pavement marking paint "
Table 2 pavement marking paint should satisfy technical indicator
In 13 test items of table 1 and table 2,5,7,8,9,11,12,13 these 7 indexs are the performance decision by resin basically, are the core index of coating.Therefore, the performance of resin has determined the performance of gage mark coating.
So, according to the industry standard of pavement marking paint, is there the UPR that meets the demands can be used as the main raw material of gage mark coating? by consulting document, data, further clear and definite research imagination.
On the basis of existing UPR technology, some researchists have made good try to the two component road mark paints of UPR preparation, and its method can be summarized as two kinds:
1) when synthesizing UP, add the unsaturated fatty acids of siccative oil or siccative oil, make the UP of modification have air-drying property, and then obtain UPR for two component road mark paints
(5)
2) adopt commercially available 191 type UPR and polystyrene (PS) solution, the two component road mark paints of preparation
(6-8)
Wherein: method 1) have significant disadvantages, the UPR that this technology obtains, though have air-drying property, but the two ends of its UP molecular chain, usually have carboxyl (COOH) or hydroxyl (OH), still a kind of common UPR is not water-fast and alkaline-resisting in essence, can not satisfy 8,9 two requirements in the JT/T 280-2004 standard meter 1, be not suitable as road mark paint.
Because method 1) tested by Quanzhou Highway Administration Bureau in Fujian Province, in market study subsequently, situation about understanding has confirmed above deduction, and this method is also unsuccessful, fails to come into the market.
So, method 2) whether feasible?
Method 2) adopted commercially available 191 type UPR and polystyrene (PS) solution, the two component road mark paints of preparation, 191 type UPR wherein are a kind of UPR by the DCPD blocking modification.
Data shows: DCPD is the ethylene industry byproduct, is the hydrocarbons that obtains after cracking c5 separates.DCPD has erosion resistance, ultraviolet resistance irradiation, thermotolerance and air-drying property, and with low cost
(9-10), wear resistance is good.With the two ends of DCPD sealing UP, make the end carboxyl (COOH) or terminal hydroxy group (OH) with the DCPD addition reaction, obtain modification UP, make UP have the advantage of DCPD comprehensively, the principle that Here it is DCPD can modification UP.Be exactly the kind of domestic generally acknowledged, cheapness and excellent performance by its UPR of obtaining of dilution
(11)If be applied in the gage mark coating, desired 5,7,8, more than 9 core index in the table 1 all to improve, therefore, method 2) might satisfy the requirement of table 1 in theory, next, whether can satisfy the requirement of table 2 with further investigating it.
Adopt the formulated gage mark coating of reference 6, the result is as follows:
One, coating snappiness index approximately be 8mm (GB requires≤5mm).Its two, the dope viscosity index is 247s, far above 130s (viscosity is higher than 130s, general spraying machine can't spray).
Therefore, method 2) with the gage mark coating performance imperfection of commercially available 191 resins preparation, can not satisfy the requirement of table 2, not a kind of qualified gage mark coating.But its useful inspiration is: with the two ends of DCPD sealing UP, in theory might satisfy the requirement of table 1.
So far, the present invention adopts following research imagination: one, synthesize the UP of DCPD modification by oneself, and make coating satisfy the requirement of table 1.Its two, take into account snappiness and viscosity with the balance gage mark coating by the length of regulation and control UP molecular chain, make coating satisfy the requirement of table 2.
1.2.1DCPD blocking modification UP
Because the performance of gage mark coating is mainly determined by UPR, and the performance of UPR mainly determines that by UP therefore, it is just most important to have suitable UP.
Use the two ends of DCPD sealing UP, can make to obtain desired 5,7,8, more than 9 core index of JT/T 280-2004 in the table 1 to improve, so the present invention determines: modification UP at first must be the structure by DCPD sealing two ends.
1.2.2 take into account snappiness and the viscosity index of modification UP
Because self sticking power of reactive resin is better, for 11 in the table 2,12,13 three technology indexs, only considers that the 11st (snappiness) and the 13rd (viscosity) gets final product.
Snappiness and viscosity are mutual contradiction to a certain extent, need balance and take into account, this be because:
1) if the UP molecular chain is too short, the UP viscosity of generation is low, but snappiness may be not enough, and fragility is big behind the paint solidification, bursts apart easily.
2) if the UP molecular chain is long, the UP snappiness of generation is good, but viscosity is just big, during owing to allotment coating, also will add solid face, filler, and viscosity will rise greatly, causes spraying (necessary≤130s, as to be coated with-4 glasss).
1.2.3 determine UP molecular chain length by viscosity index
Because the ratio commonly used of preparation coating is UPR: silica powder=(45%～50%): (55%～50%), for this reason, buy several common UPR, prepared coating with common UPR and silica powder with 45%: 55% ratio, viscosity and the snappiness of test coating compare.
Purpose with several common UPR preparation coating is: obtain viscosity data by experiment, investigate out with this, when how many times are the viscosity of UPR approximately be, can make dope viscosity about about 130s (being coated with-4 glasss), (can realize good spraying when being this viscosity because of coating) greatly, simultaneously, investigate the coating snappiness.
Find through overtesting: when UPR viscosity was greatly in 30s (being coated with-4 glasss), the viscosity number of coating was greatly about 130～160s (being coated with-4 glasss), and near the viscosity number that is fit to spraying, simultaneously, its snappiness index is 5mm, meets the requirement of table 2 GB basically.
Therefore, if the viscosity controller of homemade novel UPR in 30s, should be able to obtain the coating that is suitable for spraying, that is: dope viscosity≤130s (being coated with-4 glasss), simultaneously, snappiness is qualified.
Synthetic test through early stage exploration is found: with maleic acid monoesters (DHCM) and the PG esterification condensation of DCPD end-blocking, the UPR viscosity that obtains greatly about about 30s, the dope viscosity of preparing and snappiness meet table 2 requirement.Simultaneously, UP structure wherein can satisfy 5,7,8,9 index requests of table 1 again by DCPD sealing two ends, therefore, considers it as the resin in two component gage mark coatings.
2 experimental sections
2.1 main agents and effect thereof
Main agents specification and effect see Table 3.
Main agents and the effect thereof of table 3DCPD modification UPR
2.2 key instrument
Key instrument specification and effect see Table 4.
Table 4 key instrument and effect thereof
2.3 reaction principle
Conjugated double bond chemical property in the DCPD molecular structure is very active, can carry out addition or polyreaction
(12)Under suitable condition, it and maleic acid carry out addition reaction and can generate DCPD-maleic acid monoesters (DHCM).
With MA, DCPD and H
2O is the process of the synthetic DHCM of raw material, and two steps below main the branch carry out.
1) the MA hydrolysis generates maleic acid
2) DCPD with the carboxyl generation addition reaction of maleic acid, generates DHCM under 110～140 ℃ of conditions.
3) the esterifying polycondensation reaction takes place as monobasic unsaturated acid and PG in DHCM, obtains the UP of DCPD end-blocking.
4) UP of DCPD end-blocking with the methyl methacrylate dilution, obtains the UPR of DCPD modification.
In esterification with methylsulfonic acid commonly used as esterifying catalyst.
2.4 concrete reaction process embodiment 1
Hydrolyzed addition process is adopted in this test
(13-14)
2.4.1 it is reinforced
At first with the MA of 98g (about 99.5% content, approximately 1mol), with 134g (99% content, about 1mol) DCPD, join in the 500mL four-hole boiling flask that agitator, thermometer, nitrogen conduit, fractional column, condensing works are housed, be heated to 110 ℃ after, the insulation 30min.
2.4.2 hydrolysis
Slowly stir, and (18g 1mol), makes it hydrolysis and generates maleic acid to splash into water with the MA equimolar amount gradually.
2.4.3 addition
Dropping water finishes, and under 124 ℃ of temperature condition, insulation, addition reaction 2h generate DHCM.
2.4.4 esterification
Heat up on one side then, add the PG of 42g (according to reaction formula on one side, PG should be 0.5mol, 38g, but when considering esterification, the loss of PG in the fractionation process, the actual 0.55molPG that adds), simultaneously, generally add the methanesulfonic acid catalyzed agent of 100～200ppm (massfraction), present embodiment is the methanesulfonic acid catalyzed agent that adds 150ppm (massfraction).
Under nitrogen protection under normal pressure, constantly stir, progressively heat up, utilize fractional column, constantly separate and discharges reaction water, carry out esterifying polycondensation gradually and react, slowly be warmed up to 200 ℃.
2.4.5 control acidity
When the reactant acid number was reduced to 35mgKOH/gUP, stopped reaction began cooling.
The measuring method of acid number: get the UP of 1～2g, with the KOH ethanol standard solution titration of 0.09～0.1mol/L, add 3～4 Bromothymol blues and make indicator, when solution by the orange-yellow terminal point that is when becoming blueness and keeping 15s colour-fast.
Calculation formula: acid number=M * (V ÷ 1000) * 56.1 ÷ W
In the formula: M---the concentration (mol/L) of KOH standardized solution
The consumption of V---KOH (mL)
W---UP sample mass (g)
2.4.6 adding stopper
Treat that temperature is reduced to 125 ℃, add the hydroquinone of polymerization retarder of 200ppm (massfraction), stir 10mi n.At this moment, approximately obtain the UP of the DCPD end-blocking about 257g, yield is approximately 93%～94%.
2.4.7 the adding thinner obtains UPR
Continue cooling, when temperature is 100 ℃, add the methyl methacrylate monomer of 138g (about 35% resin total mass), fully stir and cool off, obtain about 395g brown yellow transparent liquid, be the UPR of DCPD modification.
2.5 modification UPR application performance appraisal procedure
Through above synthetic test, obtained modification UPR, next carry out Performance Evaluation to UPR and with UPR institute coatings formulated, the method for assessment has two kinds.
The one, UPR Performance Evaluation.Get the UPR of 100g, add 2g initiator (4% content earlier, cobalt naphthenate solution) and stir, then, add 1g promotor (8% content, methylethyl ketone peroxide solution), pour mould into after stirring rapidly, mixing, cross-linking and curing reaction takes place in UPR, and the solid UPR cake to make carries out every performance test.
The 2nd, the coating property assessment.With UPR: the ratio of filler=45%: 55%, stirring and evenly mixing makes coating.Get this coating of 100g, add 2g initiator (4% content earlier, cobalt naphthenate solution) and stir, then, add 1g promotor (8% content, methylethyl ketone peroxide solution), pour mould into after stirring rapidly, mixing, cross-linking and curing reaction takes place in the UPR in the coating, and the solid coating cake to make carries out every performance test.
3 experimental results and discussion
In process of the test, for the performance quality of UPR, the present invention investigates following 8 indexs: thermostability, sticking tire time of drying, sticking power, snappiness, viscosity, water tolerance, alkali resistance, wear resistance.
3.1 optimum reaction condition control
Because the DHCM that the addition reaction stage is synthetic, determined the performance of modification UP and modification UPR, final decision the performance of coating, therefore, in the addition reaction process, by change time and these two reaction conditionss of temperature, compare one by one, to obtain the DHCM of high-quality, finally obtain the UPR of better performances.
According to document, the temperature range that DCPD and maleic acid carry out addition reaction approximately is 110～140 ℃, and the time interval that carries out addition reaction approximately is 0.5～3h.Because the interval value span of these two reaction conditionss (time and temperature) is bigger, if react without optimized choice, just can not obtain well behaved DHCM, and then, also can not obtain well behaved UPR and coating, so the present invention has carried out a series of tests, purpose is to seek best addition reaction time and temperature.
3.1.1 the addition reaction time
At first, in the temperature range of addition reaction, select a temperature spot as addition reaction temperature (such as 110 ℃) arbitrarily, keep this temperature-resistant, constantly change the time span of addition reaction, to seek the best addition reaction time.
110 ℃ of fixedly addition reaction temperature change the addition reaction time, and the different addition times are to UPR Effect on Performance such as table 5.
Table 5 changes the addition reaction time to UPR Effect on Performance (110 ℃ of addition reaction temperature)
The present invention determines that the foundation of best addition reaction time is: synthetic UPR air-drying property the best, namely not sticking tire is the shortest time of drying.Can be drawn by table 5: the addition reaction time is the resin of 0.5h, and thermostability is bad; The addition reaction time is the resin of 1.0h and 1.5h, and not sticking tire is longer time of drying; The addition reaction time is the resin of 2h, its key index (sticking tire time of drying) optimum, but thermally-stabilised poor, and may to be that temperature of reaction is improper cause reason; When the addition reaction time was increased to 2.5h, the key index of resin (sticking tire time of drying) began variation again.
In sum, in order to obtain best sticking tire time of drying, selecting the addition reaction time is 2h, but best addition reaction temperature is not 110 ℃.
3.1.2 addition reaction temperature
Fixedly addition reaction time 2h changes the addition reaction temperature, and different addition temperature are to UPR Effect on Performance such as table 6.
Table 6 changes the addition reaction temperature to UPR Effect on Performance (addition reaction time 2h)
As can be seen from Table 6, when the addition reaction temperature was 124 ℃, not sticking tire time of drying and the thermostability of UPR all reached best state, and the wear resistance index also obtains to improve, and 124 ℃ is best addition reaction temperature.
Through overtesting, the addition reaction top condition that obtains is: addition reaction time 2h, 124 ℃ of addition reaction temperature.
3.2 the preparation of coating
3.2.1 determine best weighting agent
(15)
Various mineral fillers not only have increment and fill the effect that reduces cost, and can improve effects such as graticule is heat-resisting, wear-resisting, improve sticking power.
Be filmogen with UPR, successively customary filler screened, with Disposable paper cup as container, each a kind of filler of test and Selection, with UPR: the ratio of filler=45%: 55%, preparation 100g coating mixes with glass stick, leaves standstill 1 hour.The main investigation estimated stability, settleability, three technical indicators of viscosity.Its experimental result such as table 7.
Table 7 is selected packing variety
As known from Table 7: the paint stability of the various fillers of comprehensive evaluation, settleability, three technical indicators of viscosity, obtain silica powder as coating master anti-wear agent by screening, kaolin and white carbon black are as auxiliary packing.
3.2.2 guarantee the coating whiteness
Pigment mainly plays a part painted and protection in coating, and the mineral dye of white is mainly used to improve light scattering ability in coating, improve visibility.Titanium dioxide demonstrates bright and clear white, and is stable to the pollutent in the atmosphere, do not have toxicity, therefore, adopts titanium dioxide (TiO
2) as pigment.
Under the prerequisite that face, filler essentially consist are determined, by test, in UPR, add above material successively, constantly revise every performance index, finally obtain well behaved gage mark coating.
At first,, as target (this is that pavement marking paint is desired) ratio of titanium dioxide in face, filler confirmed with the whiteness value 80 of coating.
The configuration proportion of coating is: (modification UPR: face, filler=45%: 55%).Face, filler are then mixed by titanium dioxide and 200 order silica powders.Its experimental result such as table 8.
Table 8 coating whiteness and titanium white relation with contents
By table 8 as seen, titanium dioxide ratio in face, filler is 20% o'clock, and whiteness is up to standard, and the ratio that therefore definite titanium dioxide accounts for total inorganic powder is 20%.
3.2.3 improve the coating wear resistance
Because the titanium dioxide wear resistance is lower, coating wear resistance index is bad, and the fineness of coating master anti-wear agent particle is very big to the influence of wear resistance
(16), therefore, with the silica powder of different fineness, coating is allocated.
Continue to use the titanium dioxide of face in the table 8, filler: silica powder=20: 80 ratios experimentizes with the silica powder of different fineness.Its experimental result such as table 9.
Table 9 different meshes silica powder influences wear resistance
By table 9 as seen, when the silica powder fineness is 200 orders, its wear resistance 49mg; When the silica powder fineness reached 350～400 orders, its wear resistance became 26～30mg, and this moment, the coating wear resistance was better than industry standard (≤40mg) requirement.
3.2.4 improve the coating suspension performance
Under the condition that coating whiteness and wear resistance tentatively meet the requirements, find that proportion is bigger owing to adopted 80% silica powder in the face, filler, cause easy sedimentation, coating is inhomogeneous up and down, and therefore, further arrange in pairs or groups white carbon black and kaolin improve the resistance to settling energy of coating.
Kaolin and white carbon black are used for coating can improve suspension, prevents filling settlement.Kaolin also has opacifying power in addition, can reduce the titanium dioxide consumption, and reaches same whiteness, reduces cost.
Determine in filler: kaolin accounts for 3%, white carbon black 5%, and silica powder (350-400 order) 80%, titanium dioxide 12% is with coating its experimental result such as table 10 of this formulated.
Table 10 adds kaolin and white carbon black preparation coating property
Annotate: kaolin, white carbon black wear resistance are lower slightly than titanium dioxide, and coating wear resistance index is variation slightly.
By table 10 as seen, homemade coating whiteness is 81, its main performance index is close to two component gage mark coatings of producing with German DEGAROUTE (Degussa) acrylic resin (representative products: must plug with molten metal the two component gage mark coatings of board vinylformic acid), because kaolin has opacifying power, the titanium dioxide consumption reduces simultaneously, causes comprehensive cost to reduce, but, detect among the index, viscosity number 160s is (should≤130s, be coated with-4 glasss) bigger than normal still.
3.2.5 reduction dope viscosity
Analysis-by-synthesis coating the key technical indexes and above-mentioned experimental result thereof, and main composition in its key technical indexes and the prescription carried out association analysis, obtain following some conclusion.
1) the not sticking tire of coating is determined by this air-drying property group of DCPD time of drying, owing to add face, filler mixing, the relative DCPD groups density that causes reduces, and makes compare time of drying sticking tire time of drying (seeing Table 6) of UPR of the sticking tire of coating prolong to some extent.
2) because face, filler do not have snappiness, therefore, after being allocated as coating with resin (UPR), the snappiness index of coating, the resin of comparing (UPR) has obvious reduction, as long as but meet the GB requirement and can be suitable for.
3) resin (UPR) adds after face, the filler, and viscosity will significantly rise, and must control viscosity well, makes its 130s to be beneficial to spraying.
By analysis, through the big reason of said process prepared coating viscosity be: in paint manufacturing process, solid packing need be distributed in the liquid resin, if the surface of solid packing and resin-bonded are bad, solid packing disperses bad, will cause viscosity too big.
Find through consulting document: coupling agent can closely combine inorganic (solid) face, filler and two kinds of materials of different nature of organic (liquid) resin, and have surfactivity, adds in right amount in coating, can reduce viscosity.Every type of coupling agent is because the difference on the group, and surperficial selective to filler is so finally selected the corrdination type coupling agent for use.The present invention introduces titanate coupling agent coating is handled, and seeks to reduce the viscosity of coating.
Through adding the corrdination type titanate coupling agent account for coating total amount 1%, continue to use table 10 prescription (silica powder 80%, titanium dioxide 12%, kaolin 3%, white carbon black 5%), carry out resin and face, filler mixes, its experimental result such as table 11.
Coating index behind the corrdination type coupling agent of table 11 adding 1%
As shown in Table 11: one, dope viscosity is reduced to 120s from 160s, because the corrdination type titanate coupling agent, dope viscosity obviously reduces, and has reached the index that can be used for spraying; Its two, the wear resistance index of coating becomes 19mg from 32mg, obviously is better than present product (the wear resistance index of the two component road mark paints of general acrylic type is approximately 30mg).
This is because the corrdination type titanate coupling agent has improved the lipophilicity of color stuffing, makes color stuffing dispersed and consistency improvement in resin, impels dope viscosity obviously to reduce, and wear resistance obviously improves.
3.2.6 raising mixing efficiency
Find in the experiment that in the process that adds the coupling agent modulation, the coating that makes is stable inadequately on performance: have only the coating that mixes through greater than 30 minutes, various performances just can reach requirement.Not enough as churning time, descending will appear in index.
Found out reason by analysis, this may be owing to face, the dispersion of filler in UPR and cause in conjunction with inhomogeneous.Its solution is to introduce the means that ultrasonic wave is mixed, and shortens mixing time, improves mixing efficiency.
After introducing the ultrasonic wave mixing means, according to the prescription of table 11, prepare coating again, its experimental result such as table 12.
Table 12 adopts the coating property of ultrasonic wave hybrid technique
As shown in Table 12, behind the introducing ultrasonic wave mixing means, mix required time and shorten, the wear resistance index becomes 18mg, obviously is better than the mean value of at present two component gage mark coating product 30mg.Simultaneously, every index of coating is all qualified, and especially: sticking tire shortens to 23min time of drying, be better than national standard≤35min, reached the requirement of " quick-dry type " really.
3.3 the reason of modification UPR excellent performance
According to 2.6 modification UPR application performance appraisal procedures, find with detecting that through overtesting the gage mark coating performance that adopts modification UPR to prepare has reached the technical requirements of table 1 and table 2 substantially, this is because of the two ends with DCPD sealing UP, has brought following advantage.
1) because DCPD has air-drying property, sticking tire shortening time of drying of modification UPR, coating can satisfy the technical requirements of table 1 test item 5.
2) DCPD has unsaturated double-bond, can participate in cross-linking and curing reaction, and the polymkeric substance of modification UPR crosslinking curing is more closely knit, has improved wear resistance, and coating can satisfy the technical requirements of table 1 test item 7.
3) DCPD has sealed the end group of UP, has improved water-fast, the alkaline resistance properties of UPR, and DCPD has also protected the ester group of UP simultaneously, so coating can satisfy the technical requirements of table 1 test item 8 and 9.
4) DCPD has sealed the end group of UP, the molecular chain of UP is shortened, viscosity reduces, and the viscosity of modification UPR reduces, and makes coating can satisfy the requirement of table 2 test item 13.Simultaneously, the coating snappiness meets GB, satisfies the requirement of table 2 test item 11.
Through above experimental result and theoretical analysis, can prove the two ends of introducing DCPD group sealing UP, the novel UPR that makes has brand-new performance, lays a good foundation for substituting acrylic resin commonly used at present, with the coating of its allotment, over-all properties obtains to promote comprehensively.
In addition, modification UPR adopts methyl methacrylate as thinner, plays the cross-linking monomer effect, because methyl methacrylate monomer good weatherability, further improved the weathering resistance of UPR integral body, because modification UP is more wear-resisting, more cheap, made the cost performance excellence of modification UPR simultaneously.
It is as follows to obtain best quick-dry type unsaturated polyester resin coating embodiment 2 prescriptions of the present invention by above experiment:
The modified unsaturated polyester resin 43.2% that embodiment 1 makes
Fineness is 350～400 purpose silica powders 42.24%
Titanium dioxide 6.34%
White carbon black 2.64%
Kaolin 1.58%
Titanate coupling agent 1%
Cobalt naphthenate 2%
Methylethyl ketone peroxide 1%
In roadmarking is used, obtain good effect by these embodiment 2 prescriptions, have following " 3.4 " described advantage.
3.4 the advantage of quick-dry type unsaturated polyester resin coating and the contrast of existing gage mark coating
3.4.1 cost of use is cheaper
Table 13 is the different coating cost of use estimation contrasts that calculate in the real road construction, as known from Table 13, uses quick-dry type unsaturated polyester resin coating more economically.
The estimation of table 13 cost of use
3.4.2 use properties is more firm
Quick-dry type unsaturated polyester resin gage mark coating graticule coat-thickness of the present invention is 1～1.2mm, and work-ing life is longer, can reach 2～3 years through test, has good sticking power.
3.4.3 working service is simpler
When using quick-dry type unsaturated polyester resin gage mark coating of the present invention to old graticule secondary recoat, can directly spray in old coating, save construction cost, construct under the normal temperature, and can draw the graticule of making special graph.
3.4.4 result of use is environmental protection more
The overwhelming majority of UPR has been participated in cross-linking and curing reaction in the quick-dry type unsaturated polyester resin gage mark coating of the present invention, and the VOC value is extremely low, and solvent-free substantially volatilization is polluted, more environmental protection.
4 sum up
4.1 main result
The innovation is carried out end capping by adopting the maleic acid of DCPD, carries out esterification with PG again, makes quick-drying, wear-resisting, weather, low viscous UPR.Add appropriate filler then, make have normal temperature self-drying, solidify rapidly, wear resisting property is good, production and construction cost are low, pollution-free quick-dry type unsaturated polyester resin road mark paint.
Whole process of preparation is succinctly efficient, and raw material conveniently is easy to get, and is the good substitute products of import acrylic resin.This coating can be constructed at normal temperatures simultaneously, and use cost obviously reduces than hot-melting type and acrylic type gage mark coating.
4.2 main innovate point
1) use DCPD and play the end-blocking effect, synthetic DHCM obtains modification UP with the PG condensation again, and this UP is applied to two component road mark paints, does not domesticly see the pertinent literature report.
2) use methyl methacrylate as thinner, play the effect of cross-linking monomer, make UPR have the advantage of modification UP and acrylic resin concurrently.This compound UPR is applied to two component road mark paints, does not domesticly see the pertinent literature report.
3) in two component road mark paint actual production process, adopted the mixing means of ultra-sonic oscillation, be conducive to realize industrialization.
4.3 actual application prospect
During the last ten years, the annual fund that drops into road construction of China is up to more than 2,000 hundred million yuan, and Tenth Five-Year Plan Period investments in highway building total charge surpasses 1 trillion yuan, and national marking paint consumption will be above 300,000 tons in 2010.Be example with the Fuzhou-Xiamen motorway, the total length of the Fuzhou-Xiamen motorway of newly widening is about 260 kilometers, if use this new coating, once can save about 819 tons of coating.This new coating not only will be saved great amount of investment if apply, and to reducing environmental pollution, improve the visibility of graticule, the security that vehicle travels, and prolong the work-ing life of graticule, have important economic benefit and social benefit.
Reference
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(5) woods building, Wang Mingfeng, Gao Rongping. Study of Two Components Lacquer Used on Sign Line (J). road building machine and mechanization of building operation, 2003,2:14～16.
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(8) Sui is respectful, Ma Qinglei, and Guan Ruifang, etc. the orthogonal test research (J) of road mark paint. University Of Ji'nan's journal (natural science edition), 2004,18 (3): 200～202.
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Claims (1)
1. quick-dry type unsaturated polyester resin gage mark coating, formed by following raw material by weight percentage:
Described quick-dry type unsaturated polyester resin gage mark coating is obtained by following method:
1) the MA hydrolysis generates maleic acid; 2) DCPD with the carboxyl generation addition reaction of maleic acid, generates DHCM under 110～140 ℃ of conditions; 3) the esterifying polycondensation reaction takes place as monobasic unsaturated acid and PG in DHCM under esterifying catalyst, obtains the UP of DCPD end-blocking; 4) UP of DCPD end-blocking with the methyl methacrylate dilution, obtains the unsaturated polyester resin of DCPD modification; 5) modified unsaturated polyester resin that the step 4) of formula ratio is obtained drops into titanium dioxide, silica powder, white carbon black, kaolin, titanate coupling agent and carries out ultrasonic mixing 3～7 minutes in the ultrasonic wave mixing tank, namely gets quick-dry type unsaturated polyester resin gage mark coating goods;
Wherein step 3) DHCM as monobasic unsaturated acid and PG under the methanesulfonic acid catalyzed agent, under nitrogen protection under normal pressure, constantly stir, progressively heat up, utilize fractional column, constantly separate and the discharge reaction water, carry out the esterifying polycondensation reaction gradually, slowly be warmed up to 200 ℃, when the reactant acid number is reduced to 30～40mgKOH/gUP, stopped reaction begins cooling; Treat that temperature is reduced to 125 ℃, adding massfraction is the hydroquinone of polymerization retarder of 0.015～0.025wt%, stirs the UP that obtains the DCPD end-blocking; Continue cooling, when temperature is 90～110 ℃, add methyl methacrylate monomer, fully stir and cool off, obtain the UPR of the DCPD modification of brown yellow transparent liquid;
During construction, add cobalt naphthenate and methylethyl ketone peroxide respectively and solidify to form the unsaturated polyester resin graticule.
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| CN101457015A (en) * | 2009-01-01 | 2009-06-17 | 四川东材科技集团股份有限公司 | Dicyclopentadiene modified unsaturated polyester resin glass fiber reinforcement molding composition |
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| CN101457015A (en) * | 2009-01-01 | 2009-06-17 | 四川东材科技集团股份有限公司 | Dicyclopentadiene modified unsaturated polyester resin glass fiber reinforcement molding composition |
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