CN112045909A - Environment-friendly high-flash-point polyurethane release agent - Google Patents
Environment-friendly high-flash-point polyurethane release agent Download PDFInfo
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- CN112045909A CN112045909A CN202010545524.4A CN202010545524A CN112045909A CN 112045909 A CN112045909 A CN 112045909A CN 202010545524 A CN202010545524 A CN 202010545524A CN 112045909 A CN112045909 A CN 112045909A
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- solvent
- wax
- flash point
- release agent
- oil
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
- B29L2031/3005—Body finishings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
- B29L2031/3005—Body finishings
- B29L2031/3023—Head-rests
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
- B29L2031/3005—Body finishings
- B29L2031/3026—Arm-rests
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
The invention provides an environment-friendly high-flash-point polyurethane release agent, which comprises a release substance, a functional assistant and a solvent; the functional auxiliary agent comprises a flash point improver which contains oil-soluble special substances; the solvent includes a high flash point solvent. The release agent disclosed by the invention can be used for greatly eliminating the VOC problem caused by a volatile solvent, and is very beneficial to the VOC control of the whole vehicle seat; meanwhile, the working environment of workers is improved, and the safety problem is solved.
Description
Technical Field
The invention relates to the technical field of release agents, and particularly relates to an environment-friendly high-flash-point polyurethane release agent.
Background
Polyurethane molded articles such as automobile seats, armrests, headrests, and the like, require a pre-applied release coating on the manufacturing mold prior to injection molding to facilitate removal of the article from the mold. The traditional release agent mainly has wax property, solvent property and sacrificial property, namely the release agent mainly comprises wax as a release component, a nonpolar alkane solvent as a film forming auxiliary agent and a composition of various auxiliary agents; in the art, VOC emission requirements for solvent-based chemicals are strictly regulated. This presents new challenges for the use of conventional release agents, which mainly create the following problems:
(1) the traditional solvent system release agent has the advantages of large solvent odor and low flash point, generally belongs to dangerous chemicals, and a warehouse of a special grade needs to be set for transportation and storage, so that the hidden cost and potential safety hazard of enterprises in the processes of storage, transportation and use can be increased.
(2) The traditional sacrificial release agent solvent system has low solid content, large spraying amount and amplified VOC emission, and can bring emission reduction cost to enterprises along with the implementation of national emission reduction policies.
(3) The traditional sacrificial solvent can remain on the surface of the polyurethane molding product and can remain the odor of the solvent, and if the residual solvent which is not volatilized completely remains on the surface of the polyurethane molding product, the standard which is set by higher and higher automobile hosts cannot be achieved.
Disclosure of Invention
The invention aims to provide an environment-friendly high-flash-point polyurethane release agent, which greatly eliminates the problem of VOC caused by a volatile solvent and is very beneficial to VOC control of a whole vehicle seat; meanwhile, the working environment of workers is improved, and the safety problem is solved.
In order to achieve the aim, the invention provides an environment-friendly high-flash-point polyurethane release agent, which comprises a release substance, a functional assistant and a solvent;
the functional auxiliary agent comprises a flash point improver, and the flash point improver contains an oil-soluble special substance; the solvent comprises a high flash point solvent.
Preferably, the release material comprises wax material and/or oil-soluble oligomer oil;
the wax substances comprise one or more of synthetic polyethylene wax, hyperbranched polyolefin wax, Fischer-Tropsch wax, paraffin wax, microcrystalline wax, alpha-olefin wax, carnauba wax, Chinese wax and beeswax; the melting point of the wax is 48-98 ℃;
the oil-soluble oligomer oil comprises one or more of poly alpha-olefin, polyisobutylene, polyisoprene and ethylene-propylene copolymer.
Preferably, the oil-soluble special substance is a polyethylene glycol-siloxane surfactant, and the cloud point is preferably 30-40 ℃. The solvent is a mixture of various solvents, and the solvents comprise a high-purity hydrocarbon solvent, an isomerized hydrocarbon solvent, a fluorocarbon solvent and the like of Fischer-Tropsch synthesis technology coal-to-liquids and a high-flash-point solvent.
Preferably, the high flash point solvent is dearomatized solvent oil ExxsolTMD60(S) or Isopar (Isopar) an isomerized hydrocarbon solventTM L。
Preferably, the dearomatized solvent oil ExxsolTMD60(S) and the isomerized hydrocarbon solvent IsoparTMThe relative volatilization speed of L is slow, and the L needs to be mixed with a fluorocarbon solvent without flash point, so that the relative volatilization speed is increased to more than 8; ensuring that the high-lightning solvent is dried on a mold at 55 ℃.
Preferably, the release material accounts for 4.0-6.0% of the total mass, the auxiliary agent accounts for 0.5-2.0% of the total mass, and the solvent accounts for 92.0-95.0% of the total mass.
Compared with the prior art, the invention has the advantages that: the invention adopts an environment-friendly high-flash-point solvent system, wherein the flash point improver contains oil-soluble special substances, and can form a monomolecular film on the surface of the release agent composition, and the monomolecular film can seal the oil surface and prevent the oil from volatilizing. Meanwhile, the fire of oil can be prevented, the storage safety of products can be improved, the safety problems in the processes of transportation and use can be solved, and the process links can be controlled to save the cost.
The invention uses the high flash point solvent as the carrier solvent, thereby improving the solvent emission and the smell of a factory and being beneficial to the physical health of workers.
The invention mixes the high flash point solvent oil with slow relative volatilization speed with the fluorocarbon solvent without flash point with fast volatilization speed, thereby improving the volatilization speed of the high flash point solvent oil without influencing the surface of the product.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be further described below.
The preparation method of the environment-friendly high-flash-point polyurethane release agent comprises the following steps:
mixing an oil phase system: adding the mold release wax, the mold release oil and the high flash point solvent into a multifunctional reaction kettle, heating to 85 ℃ for melting, stirring while stirring to form a uniform oil phase system, stirring at the rotating speed of 1000r/min, adding 1/3-1/2 solvent into the oil phase system, cooling to 40 ℃, diluting to 6.8% of solid content by using the solvent to obtain a finished product, and preparing the finished product into wax slurry with the emulsion particle size of 0.1-10 mu m.
Preparing a finished product of polyurethane release agent: and adding a leveling agent, a drier, a thickening agent, an antioxidant, a foam stabilizer and the rest of the solvent into a stirring cylinder according to the specification to obtain the uniform wax slurry with the emulsion particle size of 1-10 mu m.
The invention will be further explained by means of 12 examples:
TABLE 1 Environment-friendly high flash point polyurethane Release agent example formulations
TABLE 2 Environment-friendly high flash point polyurethane Release agent example formulations
The polyurethane release agents obtained in examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 and the comparative examples were subjected to the above-mentioned performance tests, and the results of the performance tests are shown. The specific test modes are introduced in sequence as follows:
(1) flash point test
The sample was heated with continuous stirring at a very slow constant rate. At specified temperature intervals, a small flame was introduced into the cup. The lowest temperature at which the test flame caused the vapor on the specimen to flash on was taken as the flash point.
The test cup, test cup lid and accessories were rinsed with solvent to remove all the gum or residue traces, and the test cup was then blow dried with clean air to ensure removal of the solvent. After the cleaning is finished, the product is placed in a clean and dry place for storage and standby.
The test steps are as follows:
loading a sample into a sample cup to a position of plus or minus 2mm of a feeding line, loading a sample loading oil cup into an instrument heating well, covering a cup cover, inserting a thermometer into a thermometer jack of the cup cover, powering up the instrument, pressing a stirring switch, and selecting corresponding test steps (the rotating speed of a stirring motor corresponding to the step A is 90-120 r/min, and the rotating speed of a stirring motor corresponding to the step B is 250 plus or minus 10 r/min); adjusting a heating button, observing a thermometer and a voltmeter, and adjusting the heating rate (1-12 ℃/min, manual control); opening a gas valve, igniting a pilot fire device, and adjusting the open fire of the pilot fire device to meet the test standard requirement; when the preset flash point of the sample is lower than 110 ℃, igniting from 23 +/-5 ℃ below the preset flash point, and igniting once when the temperature of the sample rises by 1 ℃; when the temperature of the sample reaches the proper ignition temperature, the spring knob is rotated to start ignition; when a flash fire appears, rapidly observing the thermometer, and recording the temperature at the moment as the flash point of the sample; after the test is finished, the heating is adjusted to the lowest, and the stirring, the gas source and the power supply are closed; the test cup and the utensil are cleaned for the next test.
(2) Demolding force test
The mold release agent compositions of the above examples and comparative examples were sprayed on a stainless steel mold and then dried for 40 seconds. Then, commercially available raw materials for polyurethane foam were mixed at a predetermined mixing ratio, injected into a mold, and cured at 55 ℃ for 3 minutes. To test the extent of release, the polyurethane foam mold release force was tested by removing the spring force gauge from the mold.
(3) Bubble breaking device
The mold release agent compositions of the above examples and comparative examples were sprayed on a stainless steel mold and then dried for 40 seconds. Next, a commercially available raw material for polyurethane foam was used to specifyThe mixture of (1) was mixed and injected into a mold, and cured at a temperature of 55 ℃ for 3 minutes. Then, the surface state (presence or absence of foam cracking) of the demolded polyurethane foam molding was visually observed and evaluated. Evaluation indicates that: "very good" indicates no bubble broken state, indicating
Bubble burst is less than 25%, meaning "x" bubble burst is less than 50%, meaning "in color" bubble burst is greater than 50%.
(4) Odor test
The smell property: after the non-metal parts (or materials) are treated under certain temperature conditions within a specified period of time, volatile components are released, and the smell is prone to be perceived.
The detection device comprises: the temperature precision of the electric heating air blast constant temperature test box is controlled within +/-2 ℃. The test vessel adopts a sealed wide-mouth glass container which has no odor and good heat resistance and has the volume of 1L or 3L.
Note: a container vessel with the volume of 1L is generally selected, but a test vessel with the volume of 3L can be selected if a plurality of tests are required; the test ware is ensured to be cleaned and dried before each time until no odor exists.
An experimental sample piece: and (3) sample pretreatment, namely, pretreatment of the sample piece under the same condition is carried out in advance only when the parts need to be subjected to a special heating process in the production process. Generally, the parts in the supply state should be directly sampled and tested.
The test method comprises the following steps: odor test at 80 ℃, prepare test containers and check whether the containers are clean, odorless, and good in sealability. The sample coated with the release agent is placed in a container, an odorless aluminum foil is placed in the container, and then the sample is placed on the aluminum foil, so that the sample is prevented from being stuck to the container. The test vessel was closed with a lid and the sample and vessel were marked. Placing the labeled test container in an incubator at: storing at 80 deg.C. The order of storage and the samples in each bottle were recorded. The glass container of the sample is put into an electrothermal blowing constant temperature test box and stored for 2 hours at a certain temperature, and the glass container is kept in a close cover state in the period. After the test container was taken out from the test box, the rating was measured by not less than 3 examiners. The first tester slightly opens the cap, smells it, recloses the cap and passes the container to the second tester. After the three inspectors perform the inspection, the container is placed into an incubator at 80 ℃ for heating for 30min, the container is taken out and cooled to the testing temperature (60 +/-5 ℃), and the remaining three inspects are performed. Finally, each tester gives a personal score recorder to record the score. During the period of smelling the sample, the user should go out and breathe fresh air. The sample containers which have not yet been examined must be stored again at 80 ℃ for 30min and then cooled to 60 ℃. After the test is completed, the sample in the container is removed. All used vials, caps and screw threads were placed in a laboratory bottle washer for cleaning.
Grading: the odor evaluation criteria for all protocols were rated on a scale of 1-6, with a range between the two evaluation scales also occurring. Score 1: no smell; and (3) scoring 2: odorous, but not pungent; and 3, scoring: has obvious smell but no pungent smell; and 4, grading: has pungent odor; score 5: has pungent odor; and 6, grading: there is an intolerable smell.
When evaluating, the inspector should first determine whether the odor is irritating. If not irritating, a score of between 1 and 3 is given; if irritancy is present, a score of between 4 and 6 is given; if the tester records the score, the recorder records the score after the test cycle is finished. The record includes the name of the inspector and the score of their inspection.
And (3) testing: the evaluation of the odor was related to the sensitivity of the test person. If the scores of each evaluation are inconsistent and are normal, if the difference between the tests is more than 2 points, repeated tests with at least six testers are carried out again. Evaluation of odor and testing of the health of the person. The tester should also characterize the odor after giving a score. The odor score of the material tested is the arithmetic mean of the scores given by the six test persons (excluding a highest score and a lowest score). The average may also be on the order of a half point score; the approximation uses a carry system.
TABLE 3 Performance test of an environmentally friendly high flash point polyurethane release agent
TABLE 4 Performance test of an environmentally friendly high flash point polyurethane release agent
Examples 1-11 were compared to comparative examples 1-2: comparing examples 1-3 with examples 4-6, using D60 solvent oil smells more than using Isopar L; when D60 and Isopar L are used, no fluorocarbon solvent is added, the foam foams because the solvent oil can not volatilize, and the foam foams to cause closed cells; when fluorocarbon solvent is added, the baking-free foam can be avoided. According to the comparison between examples 7-8 and examples 9-10, the volatilization rates of D60 and Isopar L can be increased when a certain flash point of 56 ℃ is added, so that the addition amount of fluorocarbon solvent can be properly reduced; in examples 7-9, the same fraction of flash point booster was used to provide a greater effect on D60 because Isopar H was closer to Isopar L and D60 was more dense; when a fluorocarbon solvent is not added, the volatilization rate is affected, and thus, the scorch is also caused. A low odor high flash point release agent meeting the high flash point of 61 ℃ can be obtained by blending a flash point enhancer and a comparison of the isoparaffins Isopar H, Isopar L and D30.
The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any way. It will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. An environment-friendly high-flash-point polyurethane release agent is characterized by comprising a release substance, a functional assistant and a solvent;
the functional auxiliary agent comprises a flash point improver, and the flash point improver contains an oil-soluble special substance; the solvent comprises a high flash point solvent.
2. The environmentally friendly high flash point polyurethane release agent according to claim 1, wherein the release material comprises a wax-like material and/or an oil-soluble oligomer oil;
the wax substances comprise one or more of synthetic polyethylene wax, hyperbranched polyolefin wax, Fischer-Tropsch wax, paraffin wax, microcrystalline wax, alpha-olefin wax, carnauba wax, Chinese wax and beeswax; the melting point of the wax is 48-98 ℃;
the oil-soluble oligomer oil comprises one or more of poly alpha-olefin, polyisobutylene, polyisoprene and ethylene-propylene copolymer.
3. The environment-friendly high-flash-point polyurethane release agent according to claim 1, wherein the oil-soluble special substance is an organosilicon-modified polyether fluid, the organosilicon-modified polyether fluid is preferably a polyethylene glycol-siloxane surfactant, wherein the siloxane is preferably methyl siloxane, and the polyethylene glycol-siloxane surfactant has a cloud point of 25-50 ℃, preferably 30-40 ℃.
4. The environmentally friendly high flash point polyurethane release agent according to claim 1, wherein the solvent is a mixture of solvents including high purity hydrocarbon solvents, isomerized hydrocarbon solvents, fluorocarbon solvents, and the like, and high flash point solvents of fischer-tropsch technology coal-to-oil.
5. The environmentally friendly high flash point polyurethane mold release agent of claim 1, wherein the high flash point solvent is dearomatized solvent oil Exxsol-D60 (S) or isomerized hydrocarbon solvent Isopar-L.
6. The eco-friendly high flash point polyurethane release agent according to claim 4, wherein said dearomatized miscella Exxsol D60(S) and said isomerized hydrocarbon solvent Isopar L have relatively slow volatilization rates, requiring mixing with a fluorocarbon solvent without flash point, and increasing the relative volatilization rate to 8 or more; ensuring that the high flash point solvent is dried on a mold at 55 ℃.
7. The environment-friendly high-flash-point polyurethane release agent as claimed in claim 1, wherein the release material accounts for 4.0-6.0% of the total mass, the auxiliary agent accounts for 0.5-2.0% of the total mass, and the solvent accounts for 92.0-95.0% of the total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010545524.4A CN112045909A (en) | 2020-06-16 | 2020-06-16 | Environment-friendly high-flash-point polyurethane release agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010545524.4A CN112045909A (en) | 2020-06-16 | 2020-06-16 | Environment-friendly high-flash-point polyurethane release agent |
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| CN112045909A true CN112045909A (en) | 2020-12-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115386414A (en) * | 2022-10-25 | 2022-11-25 | 广州洛德化工科贸有限公司 | Volatile stamping oil, preparation method thereof and processing method of silicon steel sheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085542A (en) * | 2006-06-09 | 2007-12-12 | 戈尔德施米特有限公司 | Release agent and its use in the production of polyurethane moldings |
| CN102985506A (en) * | 2010-07-09 | 2013-03-20 | Agc清美化学股份有限公司 | Nonflammable solvent and surface-treating agent |
| CN103753741A (en) * | 2013-12-27 | 2014-04-30 | 上海古猿人石材有限公司 | Release agent for polyurethane rubber mold of cultured stone and utilization method of release agent |
-
2020
- 2020-06-16 CN CN202010545524.4A patent/CN112045909A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085542A (en) * | 2006-06-09 | 2007-12-12 | 戈尔德施米特有限公司 | Release agent and its use in the production of polyurethane moldings |
| CN102985506A (en) * | 2010-07-09 | 2013-03-20 | Agc清美化学股份有限公司 | Nonflammable solvent and surface-treating agent |
| CN103753741A (en) * | 2013-12-27 | 2014-04-30 | 上海古猿人石材有限公司 | Release agent for polyurethane rubber mold of cultured stone and utilization method of release agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115386414A (en) * | 2022-10-25 | 2022-11-25 | 广州洛德化工科贸有限公司 | Volatile stamping oil, preparation method thereof and processing method of silicon steel sheet |
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Application publication date: 20201208 |